t*/ y 4t "'"3\-:s ?L-t ct:'\3t2\ L' Y- -"-''1 '3t ( -z-?

D
P\ t;9 --1)
- '. rP t,i' 7, ";9 e 9? |
'eV-2 ..rL\]ij atf til ;l gL t4 -', Z..tt\ \,.*l o-9fl**J:^o^ur-u/4jluiG)\ - t

.! ,<r-E! t c,l-:- -tv 1t\) 4. clllr

'+t,6)\G;ret, \-?r- k 97rd,v q--t-
-,p-'iJ
r2
-c.eLi -^^=o* ', Jt/l tt4tdt '< '*ruy'tv-a
-$n4'.trpt C3.!3- ';\L)\ Jr-;:J1 .Yl g t -_,Uu^tt ts o? t t4 _i qa, ai\e; I _\e tt;zt'V
t71

The First Law and O -F ly;q e>vJ

Basic co"SptE' , lrb -a-or, (Jst Jl'.rD

: !*..
z&J/,ifi u

'(a k) ,NrPr'*) ).r+)t'^ttful jl-:,t-;it\ tz -',Z-Jw\ oi \tJt- E

In this chapter, we introduce and apply the fir'st law of ther:modynamics, one of the two funda-
mental laws upon which all of thermodynamics rests. Thus, in this chapter.we:

. Introduce the concept of internal energy; i.e., energy stored within a substance
Present the first law of thermodynamics, which reflects the observation that energy is
neither cleated nor destr.oyed
Develop the concepts of thermodynamic equilibrium, state functions, and the thermbdv-
namic state of a system

plocesses connectiqg equilibrium states

ure of energy store{ within a substance, par.ticularty

Use heat capacities to rclate changes in the internal energy and enthalpy of a substance
to changes in its temperatule
Illustr-ate the construction of energy balances for open systems

2.1 JOULE'SEXPERIMENTS

The prcsent-day concept of heat developed following clucial experiments cauied out in
the
1,8J9-s-by James P. Joule.l In the most famous series of measurements, he placed
klown amounts
of warer, oil, and agitated the flu ith trtatingstirrer..
The amounts r and the resulting temperature changes of the
fluid were ac le showed that for.each fluid a fixed amount
of wor-k per unit mass was r.equired e rise caused by the stiring,
and that the original temperature of t vas restored by the h'ansfer.of heat through simpl*e
thttp://en.wikipedia.org/wiki/James_prescottJoule.
See also:

L" J-<
ti

,>
t\ frv /.ti
t aLrty. ct\11sJci! -* r/'t'
,G7 llp:iir r c-r",
 ,-t\, \^/g' |p & -;.+ "4" ;W --2r-o-7-Jttb)r..1r
$.''uf \ E-3:,h-a;r,}Jr --.-D l-i t- J>p 'V
-G /vt
at p' rie. t- .9 ?v, y -tA -, )1, s/
.t-tla
o) v' -sl lJp
v'"!6tl^tr{y : W1,

Dtl z't)w- - ,G ar;-{ts 6'{t t Jl;? ?r- sP)r df -,,

-tlt . --rt-ilt2\/l _t} t*-24-7-z
",\i,
=^5;'€
2.3. Tlrc First Lau, of Thennodytnntics
" 25
<' Lt Ju|
contact with a coolel object. These experiments demonstrated the existence of a quautitative
.* .,*$tu -oliu -.t ln herween wnrk and heat and thereby showed that heat iS a folm of energy.
reletinnshin Gr6.9l
Mef*$on -7"L!.,.,J2 .s l'/r 'J.
!4 ('?,: z=
kE ttr
\ ibvalfon JSlr,.L,'L/ 4;,rr
Ft
-.' ;| ulir.tl',
otr4 -
'2 '
JP
(i,ate-w-lea.l4kr-)Frc<):-:-\
c"** ;a"'Af y.Ql
-
*""w I
^-3J
tE a tJ iJ1 Z^f2
In ro Y.

..AQt,nzJte U24<' \tn'qwt")/L\1f -' '-:'.' -

^- .- ^ fiom the
In expelimentS like those o{.|g!9, energy added tn a flrrid-a:s work is later trartsferl'ed . . | - it E
fluid ;;;;;;:il;;
as hr d"*";T:.*'gv arter its aooiiioitoland u.ror. itr-i'u*i"' r.nn, nVF)t Gt
'!iio.
*rG ftuiOZ A latio44! answer to this question is that it is contained within the fluid in another- -o-ti tl,'d t$s 1

form, whiclr we caTl intenml energy.

,6J. ^
_/-.frf-VS'2'
The intelnal enelgy of a substance does not include energy that it may possess as a . 1. ra\)
fesu]t of its gross position or movement as a whole. Rat
comprising the substance. Because of their ceaseless
energy oftlanslation (motion through space); except for
l@E:gggy'6f lotalign and of intemal vibration
in cleiGi6G*1ur rrrotion, on d thus causes an i**iGi
Wort done on the substan as was shown by Joule- The intelnal
;)t:.-J"G
energy of a substance also associated with intelmolecular forces. r. -
,
'

Molecules attract or: repel nergy is stored tlfrrrgh-ffiiliera;- JF, Q f*-zt

tions, just as potential energy of configuration is storcd
On a submolecular scale, enelgy is associated with the i
atoms, which includes the energy of chemical bonds tha
This er.rergy is named ittternal to distinguish it
associated wit oprc
which can be t , oO4ist
-- ;V
Internal thermodynam)c prini-
definition. It is a - **--
tive.It cainot be directly measured; there are no 4telilljntrgl mdffi. As a result, absolute-u,w2 ll :\ ,j- q,
values arc unknown. However, this is not a disadvantage in thermodynamic analysis because
't-lj1 <t.-z
il; ;,il;;";l""; "r g,t'n" ther- -'l''!-r\' -r
only clnng,es-in intelpal en9[gtg-19__1.9_q]!n'ed. In the context of classical thermodynamics, the
G "rffiilil;ffi;,;#a'm..-'i"i ,irU\
r

ilie-relaEiinlhip of
modynamics, wfriEn-tEatS macroscopic pr-operties such as inter:nal energy

.,, ,;:tpa'*!tz)j(^t,t,,v,Jr)3/
.T"l?:'liiglli":'-^''lqi:t^";glfl:
1"€?i's!5]"# il'irg',,B'; o.t *n? ';-'€ szy'z tu\ o-rt'
,-/Wt r.Jt -t-ll .)52:J
2.3 THE FIRST LAW OF THERMODYNAMICS

Recognitiol of heat and intelnal energy as folms of energy makes possible the generalization
of the pr inciple of conservation of mechanical energy (Sec. t J) to include heat and internal
enelgyin addi tion tojwor\ and nffiG gy. Indeed, the generalizati on
to still other
"*t"rng1p1q1ig13gft
folms, such as and.magnetic
can be extended
Overwhelming evidence of the validi its stature to
ru.
thatE a law of nature, known as the fir:st law modynamics. O". fot*glg"t"tt"glq

Although energy assumes many forms, th

stant, and when energy disappears in on
in other forms
U{ rjA{ i{'\Dt )Wl;-t) --+V'J'P '^'W '4St
(aPY)L;-t:tr
 ' }..* t U- .t! |
2.1s1 2e,t+ '?-'N:
LS; (f\t,I j:r3-4,P,4:-.,
:\Pt : gll j,!|6
-&t)_) tt 'a-€.r ", =A
'-;.t ,,:, u;dut i-Qt.* +,(
-a"-i^L>
a.l-u+, t f)g t,/o,i4
d))-r->
@ r>
.9v
Yv bl
;.I-J,;-.L -,;;;; r-, ; -i

>"*j,:t oiPr-.r t, 2tJ1, Cq .Z uUr', -rr7 -a$ y3: t.,tj,,7r,!];=

"r-!y4 fpc-r. C
zo CHAPTER 2. TIrc First Inu, and Other Basic Concepts -,il_V -:-\b) |
, f tb)t J, "'+ t t-z J*
In ro a given process, the spher.e of influence.of
isdivide srcm and its surrontdings. The legion in which :I T:::: o,e U ,,: ke- p 6 e
the pl'ocess
occurs is ; everything with which the system intelacts is its sur.r-ou1d - , 6 , ult--A l€ll
ings. A system may be of any size; its boundar.ies may be
Frequently a system consists of a single substance; in oth
event, the equations of thermodynamics are written with
This focuses attelltion on the palticular-process of inter-est
dilectly involved in the pr:ocess. However, the fir.st law app
ings; not to the system alone. Fol any pr.ocess, the fir.st law
r-' -'y
A(En.r'gy of the sy-gem) + A(EneLgy of.
U , Ft, k c_

where tbe difTerence operator "A" nges ir. the quantities euclosed in paren- "W C
in -ii ,l r ,J". t-
theses. Thesystgm may change in
in its poteDltal or kinetic,.gnergy, and .*t
i d >_ 3^/u
the potendal or kinetic energy of it
In the context of thermodynamics, heat and work lepresent energy rz transit across ' $pp 't2)) t
tlrc boundary dividing the system from its surroundings, and are never stored or contained
in the system. Potential, kinetic, and internal energy, on the other-hand,j6s+!g wiih and a,e
stoled with mattel'. Heat and wor* l'epresent energy fl.outs to or- from a system, while potential,
kinetic, and internal energy r€plesent quantities of energy associated with a system. In pr-actice
Eq. (2.1) assumes special forms suitable to specific applications. The development of these
forms and their subsequent application are the subject of the remainder of this chapter.

2.4 ENERGY BALANCE FOR CLOSED SYSTEMS

Jo =o ov/ - u f'< vtakte^r
If the boundary ofa system tem and its
surroundings, the system is
artr-Jr\leJs'G)
'
The devel_ -"3tJr)t U
opment of basic concepts in ft;.1.o
n of closed
systems. For this reason they are t e important for industrial pr.ac- ,t t')/ 62Vt
-
tice are plocesses in which matter
pl'ocess equipment. Such systems
as str.eams that el.lter and leave
5;5 J*, cs! r --1
once the necessary foundation mater.ial has been presented.
are t|eaied later in tfis'chapier.,
., i ?, l/,92 ,k
Because no sffeams entel or leave a closed system, no eDelgy associated with matter $e
is transported across the bourdary that divides the system from its surroundings. All energy
exchange between a closed system and its sulroundings is in the form of heat or wort, and the 'a3*.111,';flt @
a,t i4->*N ---.;11,
-a3V,tt _ve4
4l tt arz a,J:;J I
, fu2 ,rL{
of
is
n-
es

;,1,'&\ o,€ ,
z<
;AU: o
 r--r-. lF=o g r\,rt
Tv
= a - --(t.l) (7.2.1)
rA./< +v<
z;4 u
TT 3ua> -vi (c"ori*5; +vc Z<-ta ( Q(p*rlioa
lCa rf
'T=z^1. ,v A,l1"l a{i t Pran S51,
rz<r5i o n
VV lvr
_)
Ve our fl Vf o.i\
{- St^r.. vF,'n.14V^144
z7
\n*l)
Balance Closed
v. >v,
' >- flAJ
taken with refererrce to the surrouudings, Qru,, and l/rurr, have the opposite sigl'I, i.e., Qru,,-= -p
al)d i4/surr = -14u. With this undelstandin!:-
A@nergy of surroundings) = Qsur, * W** = -Q - W

Equation (2.1) now becomes:2 -1,'*4 'F ^tut * € + ql,-N

A(Energy of the system) +W (2.2)
= Q

[email protected]]sthenetenelgy
tlansfelred into it as heat and wolk.
Closed systems often undergo plocesses duling which onlry the intenml gnetly of rhe
.hunges. For such processes, Eq. (2.2) reduces to:
lIg!9T
Y 6--o t_-:----:----::.- (2.3)
P6'-o
whereZ/ is the total- il_ltglUgl ene: l,'gy of the system, Equation (2.3) applies to processes of .firtite
change in the inter:nal energy of the system. For dffirential changes L/: il
dUt = dQ+ dW { -=-)"y't () 4\

In Eqs. (2.3) and (2.4)the symbols Q,W, and tJt pettainto the {rtire system, which may be of
any size, but must be clear:ly defined.
the SI system the unit is thejoule.
All terms require expressioh in the same energy uuits. Iu u:J
._-totd exk-sivc
volume [email protected] energy ut os!g4-qn the quantity of material in a

system, and ale called extenslve propertiesJi?6ntrast, temperature and plessure, the plincipal 7op.t\*-s
thermodynamic coordinates for pule homogeneous nui0s, areinaepenffil6Fthe quantily of
T,,
material, and a1e known as intensive properties. For a homogeneous system, an alternative .
l vrlusi gj-
v,,u !
means of expression for the extensive propelties, such as lr' and Lr', is:
.rpt f r'.ofe,.fie,g
€ Vt = tttV or Vt = nV and Ut=ntU or Ut=nU
wher:e the plain symbols V and U represent the volume and internal enelgy of a unit amount of
material, either a unit rnqqs ol a mole. \"9:jtr .t-prrrfic ot molar propgtre.s, r-espectively, and
they are intewiue, independent of the quantity of matelial actually pros€Ilt,
-
Although Vt and Ut for a homogeneous system of arbitrary size are
extensive properties, specific and molar volume Vand specific and molar
-
internal energy U are intensive.
,S- -t ,--.1
Note that the intensive coordinates Iand? have no-q!9rrlgc9ffi-terygts.
For a closed system of n moles, Eqs. (2.3) and (2.4) may trow be written:
I
A(nU)=nAU=Q+W (2.5)
,/
L 'ouc'r''e'Ptt)D d(nU)=ndU=dQ+dW (2.6)
hlrdY
2The slgn convention used here is recommended by the International Union of Pure and Applied Chemistry. How-
ever, rhe original choice of sign for work ard the one used in the firsr four editions of this text was the opposite, and
the right side of Eq. (2.2) was then written Q l/. -
.......-,._- - ^"---
W<rvK ', -t Vc (Ir) warR do\e on k ,y|i<r^a ( Va^"^ (vl*itid )
-Va ( e *4) Worl ot*1 t5 tr<c!J+(. ( Vs,*o,t 7Vs^r+r*\)
 -^l), a ,- tF$' ?** '>r $ ,F, a.r3 -ZI = *r t $- .et -i AXio'*
)Jr ^J \AJ!
1y I 1

"f qJ\ Z? ,..,- !tu ^f t1J\ -Qt*'tY =W

CHAPTER 2. TIte Fit'st l^aw and Other Basic

In this folm, these equations show explicitly the a4gg4-ofuubstarrce compr.ising the system.
The equations of thelmodynamics ale often written for a replesentative unit amount of I

matel'ial, eithel a unit mass or a mole. Thus, fol n = 1, Eqs. (2.5) and (2.6) become:

AU:Q+W and dU=dQ+dW

The basis fol Q and i/ is always implied by the mass or number of moles associated with the
left side of the enelgy equarion.
These equations do . Indeed, they presume
plior affirmatiou of the ex elgy, as expr.essed in the following axiom:

/.r'n io- /.' There exists a form of energy, known as internal energy U, which
is an intrinsic property of a system, functionally related to the measurable
coordinates that characterize the system. For a closed system, not in
motion, changes in this property are given by Eqs. (2.5) and (2.G).
.r_J. Equatio's..l3l
Dquatrurrs Y!) and ano
JZre) not notonry
only supply rhe means for gallglation
.)tr "lft' rrom
$!)
experlmental
suppry the
measul-ements, but they also
galsglation of clgrges
uD to
crg?g€s..ih
;Yip.r''-Ui9'xg-9!9l'gy
r' . 9 - ---- 4rov enable
vuAulu us delive lul
LU uEtlvtr fur.thf.
Lllyt
.J" Q'.^ -.--4 property relatiotrs that supply connections to ::eadily measurable characteristics (e.g., temper-
Y.l,t, .**."
ature *'" pressule).
and y' Moreover,
eoDurw,,. rvrurEu ver they
Lrrtry have
rrdvs a_99?!l!glp-o!e,
. >l,r ,' ldUal pqrp_ole, because
.J ' a oecause OnCe
once lntefnal-enelgy
internal-energy ValUeS
values
'1. *- '"'-""' theyprovide
L'uJ lJrvv.ee fol
rvr the
Lrru calcula_tion ur
u4ruur4uw of he-at andvor-k quantities
iltr-dL dllu.wu.lK qualltltles for.practical
IOI pfacucal pr.ocesses.
oo , ? 1.
, . .t- ,7 $o*n, pIOCeSSgS.
gV ",t2.' Having accepted th" pr"."dtng ffi-- i'ilassociared definitions of u ,yrt"ii-ina i;;:";;;;;;-
Q, Axiom 2; (The First Law of Thermodynamics) The total energy of any
system and its surroundings is conserved.
These two axioms qannot be p!-qven, nor can they be expressed in a simpler way. when
cnanges rn r
changes I with 4.{i-om_ 1, then Axiom 2 is universally
observed to these axioms is that they are the basis for.
lormulatton
formulation
formulation __tt number
numher of processes. withnrrr pwnanlinrr
nrncesses Without exception, -
they pledict the behaviol of leal systems.3
'//?'

' .
.t Yv) \ .\€=, tt tt',\ \ J ',|.\- -t'-,,2.2
m Canada, flows from Lake Er' s
! = f oo
eqoJ$_fq! m. Most tnii bi"';
"r

/tf ..; .*v'

j -'' '

3For a down-to-earth treatment

designed to help the student over the very difficult early stages ofan inroduction to
thermodynamics, see a short paperback by H. C. Van Ness, IJnderctandingTllerntodynanics;Doverpubljcations.com.
 Energl' Balartce for Closed S

(o) what is the potential energy of the water flowing out of Lake Erie, relative to
the surface of Lake Ontario?
-b-- tn- *
(b) At peak capacity, whatfraction of this potential energy is convefted to electri-
cal energy in the Robert Moses powerFiiffi
(c) lf the temperature of the water is qnchanged in the overall process, how much
heat flows to or from it? A-f** s

Solution 2.1
(a) Gmvitationalpotential energy is related to heightby Eq.(1.8).lith 3 equal to its

standard value, this equation yields:

' /

EP = nu8= 1 kg x 100 m x 9'81 m's-2

J
= 981 kg'm2's-z =981N'm = 981

(b) Recalling that 1 kW: 1000 J.s-1, we find the electr-ical energy genel:ated pef kg
water is:
87"19t 6
)*-e- 2.3x106kw -A1/,.tr,\r/.".r.n-l
c)"{.fuetF = 42 kW.s'kg- t ='7 42 J'ks--t
-11^r1
0 :7
|

5'!stn*

For each kiloglam of water,

T) ;l
- ?b 9,",\
t- Q=LEp-W=-981 +142=t-239J "''zzvt
{
This is heat lost from the sYstem. nut*
ir.rr-'i

//.t,)
 CHAPTER 2. The First l-aw and Other Basic C,

(g) How much electrical energy is produced when 1 kg of air pas.ses through the
IUrOrne a

(b) What is the power output of the turbine?

g!"u! transferred to the air, and if its temperature remains

(c) lf there ir

-"
unchanqed, what is its change in speed upon passing through the turbine?

*Cp,'--ti;'4-"'iY"ft'o'"
s.r; /
(a) Tbe kinetic energy of the wind on the basis of
!$ of air is:

- =
Ey,
I " (l ke)(9 m's-l)2
2tnuz =
7 = 40.5 kg.m2.s .2 = 40.5 J

Thus, the electripal energy prociuced per kilogt.am of air-is 0.44 x 40.5 =
(&) The power: output is:
17.8 J.kg-t x 15,000 kg,s-t - 267,000 J.s-l - 267 kW
(c) Ifthe temperature and plessule of the ail are unchanged, then its internal energy is
5tJ=o
_yr:Sirglfpd. Changes in gr:avitational potential energy can also be neglected. Thus,
with no heat transfer, the first law be€5mes rb --" (ar<;-5 -r
.--/
e=i A(h'netgy of the systerr) - LEy- Err- Er, = I4l= -17.8 J.kg-l
6ur
Er.r= 40.5 - 17.8 = 22.1 J.kg-t =22.j N.m.kl-t -22.7
^2.t-2
a
u^
Exr=*-22.7 m2.s-2 and u2=9.'1y',s.s-l

.26 rr.s-I. . ,. t. u, - ,.( ." ..

t*.w.tt
,/.' (). : -r;,rF,4 t ,, t;',^::;!,"f-."ui*,'-'oi,
,

2.s EourLrBRruM AND THE THERMoDYNAMTC srATE dr*lc

Jl,t'-i' r'e;1-'"t'-'rj'd
i; :':1 -)-2.r-e
"a.F
t

Equilibrium )Ft'.'o
nditio', the abserce of change. In ther.modyna ir'O1'7,:,' ,2
^i"r" _.-'-t'r\iu'jr (V-/tq
itmeansnot uttheabsence of anytendencytowardchangeona
macroscopic toward change is caused by a driving force of on" :L (' *r'6" ,-r'r-t, y*,:
kind ol anothel, indi
Hence, fol a sys tin
Different kinds of driving forces tend to bring abo
ple, imbalance of mechanical for-ces such as pressufe o
--'.L-
fel as work; temperature differences tend to cause the lc t- - ':
potentiala tend to cause substances to be transferred fro
'-t), -
all such forces are t" b3]""9e
'a *"'
aChemical potential is a thermodynamic property
treated in Chapt

.t ". .'
1c:l: ; ,)iSiblt b-'t',.- n"1." ) q-g(
_'
f4qcro
- -
:,,-
7'^/) YJ ilr<t*l ?''"6' 'j."
*\ L: ,-
Ar', ' .

"k-L
 6t's'\ Jt s-{}s& :}r i" L)GJ\ vk;* J)lt f '*v gi"=J r
c, ,) u., Ji s, , J4_r{*:J 1 .v t-, 41

14 z-j+ (*);j\ )'y,r-t1 w* o-ft{/t' iV, -f +6,wru-bt Q2v2?--t }iz'r 3:-:t q,

,rtni u/
,,-rin- & ut
-, 4'" a)J-*"!+},?vr 5-y-.*i/toLFoj
4'-'-a)J'"t"!*-;,?vr y'^b)/, u ios\\it'n:' v-/ P-'-'-r
2.5. Equilibritnn n' ' li-n (WJ, :G , .4.;fi 3,o3-<
and the srarc ' : 9a{t: }t
a2ti;-!^-e-o \
occurs in a sysrem,,?or.at equitibrium depends o,r rlsistance
I5,1.:,:,:*:1e_acru*ty

arc unifo.m rlx-oughout rhe sysrem, and

_c-q11f_o.r.in. ra. i"ilr*ii.g;; ll;
Axiom 3; The macroscopic properties of a
homoge nerfiu{Frw'ivstem at
internal equilibrium can be expressed as a
funciion of its tempeiilt": ,/ ,".,_\j,,.rj €
Qq PvT qL&-f -#Y'-rt r'e v'; \ \' t'1 ' \ "
!
model that excludes the influeuce of fields (e.g.,
s surface effects and other less common
effects.
ctical applications.

not oniy p, V, and ?, but also internal ener

(2'6) s
on the
itReci
fixing
sfafe Fnr evamnla -i+-^^^- -^^ -^

twostatefunctionsareheIdatfixedvaluesthe,t.,o,',")'))*ffiyWDuuJLallce'lIlj!
'ndvnnwin 't^|' ^c+L^ ^"t^'ance is rully
a'ce rs fully
determined.5 Th;" means rl"^.
determinerf 5 This
-o,-" ^llll-?..---,
state-function
that a li
I I

'#.]^:.X^"^ ***X*::-^-'*',ijlli#"-trapressedmathematicaryasaru il#i"":n ii I

i? \',t-, (inl-,, lio) s+));t,'. i,-, >nf

i,&',
ot\&a r.:it" )\o.,. t 3.ok ?tts f.i:r\a),
Js Yt 6tA nle)'t .'t,.r, * ;;' V t'?t j t 4P
;P;a r,4 G,o.jJ 1,,4e L-1^:' F ts \-l' t e*
 . 32 CHAPTER2' The Fi
b![
On the other hand, the tems on the right sides of E
plopel'ties; they account
,fearland work quantities, ale llot
rFounaittgsJhey depend on.the natutt of the priccess,
_g1,aph, as
of time is
of a state
gration of such a differential r en tlo of its u?lu.t' .rq.,J,
t rul1' _ ^q_1 fr L3 i"t \
-.:96.t:? Y'
.) -t)^ li , it.,., -r,\. 1*->

.uutfiniteffi\
+ / \=-----
,
J,
*\v'-' ti'n?uz"cv'
"/ J
ldw=w
r

For a closed system undergoing the same ch

cesses, experiment shows that the amounts
differ for different prbcesses, but that the
(2.5)l is the same for all processes.
'This is the basis for the identification of internal
value of AUris giveu by Eq. (2.3) regaldless of the pro
the system is between the same initial and_final states'

.
.ffi;,
Lr /^
a,,^\) . \ \.
;.:'i-e..r,-

Example 2.3
A gas is confined in a cylinder bya piston. The initial pressureof thegas is 7 bar,
and
place by latches' '"-V'/ S-
the volume is 0.10 m3. The piston is held in
ed in a total vacuum. What is the energy change of
r,,
-! ;J r ,',r (o) The whol
/r-'.'.
/_ ... j_) the appa ing latches are removed so thatthe gas suddenly
'

-.-...re-| -:l
i-r*t' ygqmg, the piston striking other latches..at the eird
""punO,
of the Process?
(b)Theprocessdescribedin(o)isrepeated,butinairatl0.l.3kPa,ratherthan
in a vacuum. What is ihe energy change of the apparatus? Assilme the rate of
freaiex-tiange between the apparatus and the surrounding air is slow com-
'pared
with the rate_q! w!'c1r the proces:-o999/s. I r> ,1 : rr
-- r LV
""rUtiy:'7s']':1 )A\; *'v\'-l ""
"'-'r''
Solution 2.3
Because the question concerns the entile appalatus, the system is taken as the qa1 pistol
aud gdil4e_r.
 2.5. Equil.ibrium aid tlrc Tlrcrntod),namic State 33

/,
$5tt'?d-:" y -$1, ,rj'$ S
.f
!( f'' {Y Y(,
ss, because no force exter.nal to the system moves,
thg.ygcqum surrounO-ing the apparatus. Hence e
y of the system does not change. Without further
bout the distr-ibution of enetgy among the par.ts of

,,-d
LF" ent of the piston, A/ = AV|/A,
sphere. It is evaluated
::*:*f,#ffii
where A is the arca of

---
--1(
- .-.j
uf
-" (l ar >e \'F
,.dlu,.J -
'^)r- ".r4t- vr- r At D AVt=-(101.3)(0.2_0.1)
at,t ^
LNr
kN
.":"y, W=-FAl
'Y ,(r:, ,y'v.
'dlr'
=-Po*
1
kpa.m3=_10.13I.m3
m
1 pU .0
Ir. {o u!\a : L;s o., \
9wz
l:-'
,W= -10.13 kJ.I.m= -10.13 kJ
Heat transfel
-5uil'[*e
be so possible in this case,
o6Tem
pr has occun ed and befcle
appreciable heat e is assumed to be zero
in Eq. (2.2), giving:
br4, ,,)l', g.tt;v2 )//'zn{,
A(Enelgy of the systenr) = Q+ W= 0
- 10.13 = -10.13 kJ

0" The total energy of the system has decreasedby an amount equal to the wort done
on the surr-oundings.
 -t7
rfJ
34 CHAPTER 2. The First Lau, and Other Basic ConceDts

Example 2.4
When a system is taken from state o to state b in the accompanying.flgure along path
gf, 199 J "f heat flows into the system and the system does 40 J of work. ,
? ,|o:t ,

Hqr' ' oeb if the work done by tLe

along path
(o) How much heat flows into the system e'v"Y
r (-
svstem is 20 J?
(b) The system returns from b to o along path bdo. lf the work done on the systeln --r .A,..r< 52
is 30 J, does the system absorb.orllberals: heat? How much? Lj tv--
,t,t,t r b.i,E G ;-
,:
'^
t

..;r-D 'i ,//

Solution 2.4
Assume that fhe systbm changes only in its intelna] enetgy and that Eq. (2.3) is
applicable. For path aclgd thus forggp4 leading from a to D,

* = 1gqj49 = 69 1
AtJrb= Qatt Wacb
- .)uJ 7:"*
(a) For path aeb,
frY
,y
LUI"'=60=Qo4tlWaeb=QoutY20 whence Qnub=80 I ).t +''te (J*-'t
(b) Forparh bda, i'z
JJ

LUL, = - LUt"b = -60 = Qaao * WMo = Qbda + 30

rr. ,r --{L{c-Uo)
and
r J\ f
Qaao=-60-30=-90J =) -'J< lDw/ I

.Heat is therefore tmnsferred fiom the,system to!E lgfSlq$ttgs. :-l

J
 N, f \;*ar9-' o '*&; y) ? \.eg , itG-u;-r-\GiG
'24, G t, ztrlS
,/ (-,,oi
gr&t -* d.J) .j:2 L- t Qr ,"vsA- $0,,t
Jt\y'r(f S-Jr"+ Q:rirr )
.i
L*4v
b ,t,?,r-1,
V- -;"ti
G -b
\'",,?i..,lftr;
-,4;#;':;(:
-d-E,rt
24 a^A; ap -*Et, gtnJ'
,.;t:. 4Z;,1-;T LT',',f,i B
"J+Jrs4,
,$;
,r s_,_* '!€ b <W, Jr ) -:C__r,
2.6. Tlrc Reversible pro,cess e.tl: / c*=w _J r-t
,C-ue-+ G
2.6 THE REVERSIBLE PROCESS

The development of thermodynamics is facilitated

by the introducrion of a special kind of
closed-system pl.ocess char-acterized as ret,ers ble:

oA process is reversibre when its direction

can be reversed at any point by
an infinitesimal change in external conditions.

@ The reversible Plocess is idea.l in that it produces a best possible result; it yields the min-
imum wor-k input required or rnaximum work output
attainable fr.om a specifiilffi;i;
r?resents a limit to the performirrceE an actual plocess
that is never-fully r-ealized. wort is
often calculated for.hypotheti ^
because the choice is between this cal-
curation a'd no calcrirationai
':$,q!e"etffia--."u,o".i,'.tfiJi.H,tilil1i:il:rJ:il,X.rfiT;
bined with u,, rprp;i;;;
for or produced by an actu?Tiiilffi.o
Thti concept of the reve.siblell_oseiles also plays
a key r.ore in the derivation of ther_
moay'amic itiitio-risTfi's ftitniJ.oii;*fi" often 'cornpute
changes in rher.modynamic state
functions along the path of a hypothetical revemible
involving only state functions, then this r.elationship
is
same change of state.Indeed, the primary
use of the r
tion of generally valid relationships urnong ,tut"
functions. St:, "_2
Reversible Exponsion of o Gos --rgri 'gt:it,2
'
*";::1l,TJif.3;'"::,"'*":*::::,ln:::!i"fiG;-*#;,*r;#,-#,x,:'ri7u-"a

the piston assembly osciljates, with, decreasing

ampirtuae,-uttimatery co
equilibriurn positio4 A/ abovb the oll. , I

3ut fecSuse
the viscous nature of the gas I
",. "",::::,:1jt:11,T^d,iTp:-a

';J'l'''s.6 massleadstopistonos"ittutio,rsoi;;ffiffi-r,#""1THffi:::::i:,#ffi1'
't9t ''$ - Jt''
/',2'6v ' '/v
However, one may inngine aprocess wherein
,*ull *us increments are removed one after
Tri;:ft,
,-a
-.f \$c;,
U I'trI /?
' .z'z 6o*nriiari.,o a-ar,,^i- ^. rL^ -^,^.! aiP , Lx :
.'7
,

,o* o, '*i[,r]i
'/ 9''',')'r'
'o'il*f;:,T"lj1:il:,ij,T':*:*P.s
m;''ootnamics' aand is rreared in Chaprer 5.
thermodynamics,
between e',ciencv and ineversibiliry requires use orrhe second ,
r'Q "4jirr,9
,,,5, l,Q -Z/,*.tg
"ds)_,r4.'LriJ
J,
v.
,\U .l
Jr
 CHAPTER 2. 71rc First lnw and Ofher Basic

Figure 2.1: Expansion of a gas. The nature of reversible

'-t-=
processes is illustrated by the expansion of gas in an
idealized piston/cylinder arrangentent. The apparatus shown
is irnagined to exist in an evacuated space. The gas trapped
=3J
jnside the cyJinder is chosen as the
system; all else is the
surroundings. Expansion results when ntass is removed
from the piston. For simplicity, assume that the piston s)ides
within the cylinder without friction and thal the piston and
cylinder neither absorb nor transl.nit heat. Moreover, because
the density of the gas in the cylinder is low and its mass is
small, we ignore the effects of gralvity on the contents of the
cylinder. This nteans that gravity-induced pressure gradients
ln the gas are very small relative to its total pressure and
that changes in porenrial energy of rhe gas are negligible in
comparison with the potential-energy changes of the piston
assernblV.
i\ -:.g \-I.e'J \
'
f \t'-3-- :,,,t;e''.;,
tl*(-:+-

another at a rate such that il. O,rron', r'ise is continuous, with minute oscillation only at the
end of the process.
nfinitesimal masses from the piston is
by a pile of powder, blown in a very
ton riseS7T7Tir-form but very slow
levels. The system is never more than
m equilibrium with its surr.oundings.
the direction of transfer ofpowder is

,,.' originalprocessapproaches reversibil.ity.

Without the assumption of a fiictionless piston,
If the piston sticks, a finite mass must be removed b
equilibrium coffion r;-essar.i to r.ever.sibility.is not
two sliding parts is a mechanism for the dissipation of
This discussion hu"..nter.d on a sinsie closed
in a cylinder. The opposite plocess, comp,.eision oi a
the same way. Therc are, however., many processes tha
than mechanical forces. For example, heat flow occur.s
electr:icity flows under the influence of an electromoti
in response to dr.iving forces that ar.ise fi.om differ.enc
of chemical bolds in molecules. The driving forces for
substances between phases ale complex functions of te
as will be described in detail in later chapters. In genera
 2.6. TIte Reversible process
JI

force driving it is infinitesimal in size. Thus

heat is transferred reversibly when it flows
finite object at temperature r to another such object fiom a
<^* cAeJ''4'A? )t"4)47 F'Jt at
temper-atule T - dr.

')?1,.,V-*,, ev-02"h 14,, ,,t, )tF),a'o.f, r'1@^

Q'-a ' ) | ) G 2 Reversibre chemicolReoctron g'
;,l't ;:,av,trs'j 2 d;,y,( v tnr-z a,
-,i-r{ r t6
action is illustrated by the decomposition
-\
oxide and car.bon dioiide gas. At dquilibr.i
lon pressure of CO2 for- a given temper.ature. Th
rvar redulf ur ru uero m oaralrce
equilibr.iumi UV ,t
1rn ct ,At__r, ej
conditions, however slight, upsets the equilibrium-and"ir.rffi;;'#"6;'Or;'Jir,r*. o1
e'1.:
,;#ff; 'r v'tr - :-' {uTrlg-l
causes ttre ,eaciion
rr to
Lv
direCtiOn Ol the Other. vrvuuuu ' _|
-l

- -:",
and the resultingi process
rrveloJ rr
is elLtrrurrBry
exceedingly stow
slow allo
and reverslble.
rever.sible- .
,(b4lh) 1JtJtozl10.;5J/';t-t 'N ,;?_l) a.\ -l -4 t j),)sli_
,.
qU r:o.lf
z-,(.\,?\
-
L.'tJ, ! '2- Sa3 thzi $\ @
iui,A ,'J-+'-*, ,-:.'4t€O
Figure 2.2: Reversibility of a chemicaf u!.'
) un, t

?." .
reaction. The cylinder is fiu"a *iif,-"..' u;;e-' tri :ilal , i

temperature is adjusted to a value such that

)i C,, , a-zz>l
the decomposition pressure isjust sufficient to .i, -'
- ,,
uj'\b\<'b?
balancethc*,"i.hr^.rr-^;".i-
balance ^^^-;;:-
the weight on the piston, a condition of"
)\
rnechanical equilibrium.

,'!!.rr'4* u] ie}:-l ,-+F- n.o ); ,-a32 '> ,?^e'

:?T:*"#l':11"*T*i::1i,':':'l:qflil;Gii",il.ffi ;?*"^,",i",
po,tenriar ain"."n.Ero-iffi,;:;;';il."*,"*
*1v-,1""i"11*j:r:::.^lt,ll ---'^ v' v/rq'r'rw' w'u'4 etr'uurrrlstlrlg
of two electfodes, one of zinc tgiedtt. other'.of
ind the
uld ntr,., platinu{n, is immersed in an aqueous
^^:A tL^
h'rrrnal,r^_i^ acid,
hydrochloric +
the t.frGn
^r.rJ.,, solution of
that occur.s is:

Zn +2HCl H2*ZnCl2
=
The cell is held under fixed conditions of temperature
and pressure, and the electr.odes are
connected externally to a potentiometer. Ifthe electrt

-1,-;,';V'.rrrrrggtcuuOlrlotiveforce(emf)producedbythecell
 G,!-r-1 fN I -'J rv'r,L!,v ilj) \ +''!4 ) t -';-r r .-)l i.v. \
q\sGaJ,,,
,. ! r
^4,,u,/'LG "a-' ) -'-
, !-,.., ,-t;Z {-l b,-' -'\L''y,"\;u-'*--:'-}'6'r di+ Oq 'L''''t'{'''-'JLt (l g'!'>
-J;lP c'Y!"1 ':Ldr -4'-ds c-Ft.' L'
7T J;',7r,"'-i" "!.4 '4"G'41;-P
4"I,\J
,.
38 CHAPTER 2. The First L'aw and Other Basic Concepts

is exactly balanced by the potential difference of the potentiometer', the reactioti is held itt
equilibr:ium. The reaction may be made to proceed in the forward direction by a slight declease
in the opposing potential difference, and it may be reve::sed by a corr:espouding increase in the
potential difference above the emf of the cell.
-, &.t,,ty',-,-:--\L;1 c)"< "'Jrr:,'',2;l o

\ v "r.:. ..-J,
Summary Remorks.on n;1egrO/e Plocesses . , ,\:ul2:-al . )
k r --aitj-" \ v q --t'*.r:i-
,. q;
<v?P:c"'ptr g' t' ;'tifi* 4
A r-eve::sible process:

a . cunbe reversed at any point by * i"r;i;Jb# i*; #,X:;,m"( ,"u ::::,';:;: :.

u'iY'- lc ^-:
6 . t*ever more than minutely removed fi'om equilibrium :,;,.',, 6---^: <C
,ti1 . Ttaverses a successiott of equilibrium statest-'?<ici!a':.'
' c Yl <.t
"&. ,rfrictionless
fi.;'t . Is dliven by forces whose imbalance is infinitesimal i
.iij . Ploceeds infinitely slowly
,.1 . Wh"n revelsed, l'etraces its path, restoling the initial

, a,- yj ), 4 tbl.lL',=t t{/ /<4 \;\, -t-?J, t ilt---",r-,,; g |,,i" \,,: t

r-,'(i,^t'-=r'
Computing Work for Reversible Processes
Equation (1.3) gives the wort of compression or expansion of a gas caused by the displace-
ment of a piston in a cylinder': 't i- f I tr
1,e , ;,,, t.,
:_lr,

dW = -P dVl
The wor-k done on the system is in fact given by th
characteristics of the relrersible ploceqs-Ap- Le-iLi?,ed. fb-e
tem be no more than iufinitesimally displaced fi'om a state
telized by uniformity of temperatule and pressure. The system then has an identifiable set of ; .-s-.|
pl'operties, including pressure P. The second requilement is
,iutrulqs_ll-aUy displaced fi'om mechanical equilibrium wit
the intelnal pressule P is never more than minutely out of ba
we may make the substitution F = PA that tr:ansforins Eq. (
which these requirements are met are said tobe mechanical
inreslared: (y't.tJ=FdL.fl,?.)
vt- n t/ fvi- -r/t - .rf ."'^:rr
p,rf (14\, -.\ t,, rr,,.r'r.^(J,r
n

Vl'_,.1 V *=-/rrrout--\ a ,..,, ^:qr.- Q.4)z^4-,(-.&,,,

r : -, (1.." ! \ 21t-p' q)
T-fq e-qgqtlqn gives the work for the mechanical-ly revetrfblgglPgryign-o-r comPression of a "- -riyu
fluid in a pistodcylinder at'rangement. Its evaluation clear'ly depends on the relation between ,+ ,, l' ..,1- ':". .i \-
P and---J i.e., on the 'p4!{_.J!h"lI9g9S, which must be specified.
l- Y, : P{"a lh:-,.tk:lgl liir-i;llourl ),r+l\
irreverlible process for the same change in \/, one needs an fficiency, which relates the actual
;woIK !o the reversible wor:k.
'i'/'!"
,) 47.' ,,,.. ,,rlo,t\' 'i"(':'!
-:-
Yc J', ,/i\'! \r '11 ovlr -
 2. 7. C lo s ed- S)t s tent Rett e rs ible P ro c e sse s ; Enth a lp1, 39

Example 2.5
A horizontal piston/cylinder arrangement is placed in bath.
The piston slides in the cylinder with negligible friction, olds it
in place against an initial gas pressure of t + Oar. f-ne init 3. The

Theprocess as desc'ibed is mechanically reversible, alrd Eq (1.4) is applicable. If

PVt = k, a colrstaut, then p : k/v . This specifies the path of ihe pr-ocess; and leads to

w= - J["i p4y, = -o. fvi dv, vl

t/i J', * =-ktnfi
The value of ft is given by: ,. .:--, _ ,c5 iq.-..r
k=PVt=PrV'r= li! x 105Pax0.Q1qr3=42,000 I
With yi = 0.03 m3 and Vi= 0.06 ms, Vj= z -l I

W = -42,000Ln 2= -29J12J
The final prdssure is

= Too,oooPa 7 bar
"=i=3#
were the efficiency of such p'ocesses known to be about gI%.K. could
,,tto 1 . r,. '
-.\'.::'
multiply the r-evelsible work by this figure ro get an estimate oift-e irreversible
work, narnely -23,290 J. f? \,\.{e. 'p. /.-'
r\tc'J1 /; -i 1
i Y:j__* ] r'"'\:-) l-71'>-)
; l. 11,-s r t '/- j3..",/.,.;.
t
frqer<\1J\C.{.}r'1--.
=. - ?,1 1yn , l,'|
2.7 CLOSED-SYSTEM REVERSTBLE PROCESSES; ENTHALpy
) -.}r'
\\/e p'esent he'e the analysis of closed-system mechanically reversibre;#Jr'{fi,;:;u-r
processes are of little interest for . Their value
lies in the the calculation of chang for a specific
change of rial process that brings about a particular.change of state,

seful and impoftant for this purpose, even

though close approximations to such hypothetical processes are not often encountered
in practice.
For I mole of a homogeneous fluid contained in a closed system, the enelgy balance of
Eq.(2.6) iswrimen: J(r,,frr ,= yl /t\= J q+ )nL -__z.s
dU = dQ+ dW
 CHAPTER 2. The First lttw and Other Basic Conc

The wolk for a mechanically leversible,gl.osgg-sy$qm pr.ocess is given by Fq. (1.3),

into th" pi.6.aili-.q,iliir.r ut"fat'
written: dW = -PdV. Subsrituii;;l-on -'-* '\ heLe

dU = dQ - PdV (2.7)
This is the general energy balance for one mole ol a unit mass of hornogeneous fluid in a
clo-sedsystemunder:goingumechurri"alFGGrsibleprocess.
fO for a constant-volume change of state, the only possible mechanical work is that asso-
ciated with stirringglgTlllg, which is excluded because it is iih6ientiy iffirsible. Thus,

dU = dQ (const V) \u)--or)/ '& \b) | e.8)

Iritegrationyields:
co'4{ -u
.,,,r.'li, ! "f3{
.:.,1i,1,'
-"i+r v,-il , '-- LU = Q (const V) 7{" " ' ' (2.9)

f!9-l!!.j!gl-.ft"_.gy th-a-nge for a mechanically levelsible, constant-volume, closed-system

process equals the amount of heat tlansferled iuto the system.
..
;2;, For a constant-pressur:e'chang-of siaiei

dU+PdV=d(U+f9=69
.A
The gloupl/ + PV natur:ally alises hele and in many other applications. This suggests the I V\-: \/'4 !

definition, for convenience, of this combination as a new the::modynamic property, Thus, the 7

mathematical (and only) definition of enthalpyT is:

., \,' \, : Y.x t: t,
a/V^alr ' ,iir-'Dl
l-' ')/*'of
C ,d, V r { .-).+ .t,1, ot1^;1"7 it - it. ,r':':
\): J/*',t , J/mur: -l (2.10) , 'l'
"'t't"
il.'A .l\'
-
whele,F1, u, and v are_molq1_o1-g1!q-q-a9s values. The preceding energy balance becomes: ,rrl ',^{ .'l I

dH=dQ (constP) "i , r-..--,.\i /.ti>it eJl)

Integration yields: l' l-r (I r I Q
,- 'fL'
\,.o.f
L,H=Q (constp) (2.12)
The enthalpy changgrll a mechanically leversible, coustant-pressure, closed-system pro-
cess equals the amount of !y-s!ep. Comparison of Eqs. (2.11) and
(2,12) with Eqs. (2.8) and ( lpy plays a.r.q!q in constant-pressure pro-
cesses analogous to the intemal enelgy in constant-volume processes.
These equations suggest the usefulness of enthalpy, but its gleatest use becomes fully .\i'. f'!' .). .f-
apparent with its appearance in energy balances for flow processes as applied to heat exchang- .-1i
" rb) ,o; .i .. )-r
1
"k '
ers, chemical and biochemical rcactors, distillatioii columns, pumps, compresso6, tur.biles,
engines, etc., for calculation ofheat and work. \, 1 oj-{,}).- ! rd
The tabulation of Q and' W for the infinite auay of conceivable plocesses is impossible. - , r*!. t.. I :-- I /+r r' r t-'r
energy, and
stance, their' 4 r$' ,+" ztl "tl:Q
of Q andW t Jl ?P"-' f)nn ^ '.-.' t

Lt- si rra ..' ', .. \- ' 2"

'l
'a
?Originallyardmostproperlypronounceden-thal'-pytodistinguishitclearlyfrom :"^' ' "t
etlttopy,apropertyintroduced
otr i , d , V .L.
Kamerli
in Chapter 5, and pronounced enlrro-py. The word enthalpy was proposed by H.
l9l3NobelPrizeinphysics(see:http://nobelprize.org/nobel_prizes/physics/laureates/1913
/i,,r_\,J_.,{i.r+,irrea.
"'".:,-, :
F_.o a, ,.,n <AL-Y
u,) d L" lp L: o4J I (i \- t;i4 s
, ; -l.!, .. ir r l-.'r-' o-t"r-'-Y
 2. 7. C Io s e d - $t s r e nt R et, e r s ib l9lro c e ss es ; Ettthalpl, 41

dH=aya41pU, (2.13)
This equati LC!,effgqgl {"te. Upon integr.ation, it becomes
an equation fol a

AH=AU+A(PV) (2.r4)
Equations (2.10),'(2.13), and (2.14) apply to a unit
mass or.mole of a substalce.

I
Example 2.6 ,
Calculate AU and LH for
]{g-_91^water when it is vaporized at the constant tempera_
:T^" _":**:_
a n o.t[e
-lstTlj&*
-orJ
q i g
I !!pa. rh e s p e I m ; ;;i,,.n or is u i d
",
I

l;::::::1,:l_.,,-,1r:^.::"-.-,,,,::1^.1i9oolo+ano r ezs -s.a-i,iespectivery. ror

this change, heat in the amount of kJ is added to the ]116.9 wate'r. ). ,.:.
), -:'^3y
,--'o\ ,t)
a*\ eSStd\
'*Y ltPz: "t ; \ 9, v v!':.1
"rVY Solution 2.6
( '// s'\:V jtr Jt-
i,"; q .(,', We take the I kg of water as the svstem heearce
imagineitcontalr"
imagine it co'talre
it alone rr
is ur
of r,Lsrcsl'
--::1':rrurr'LcrcsL'a'owe
a'd r,
interest, allu we
piston that exerts a constal.lt
s"',*"""
'.'l4l ,z
JA'
"ra-t"'-
pressur€ of_l!],]3 kpa. As heat is a
{C - t'l\
'?t
u.3,'1.1.,,r?
i'tt t ,
ilitiiiTie#iilli"l"#':f '*,
i'f
I kg
\5
:;':-: rAl
"'"11"*i"i';;1:; 2- APr,/ i,l-.-rL
system is:
/t
|
"/
I t'\ ::?
e1y' )"-' l, '/:
AH = Q=2256.9kJ . h\1, "" -J, <t
igt,'3, ^)/,
By Eq. (2.14),

AU=A,H-L(PV)=LH-pAV
'
'N ,,'!\
'.avt' For the final ter.m:
p AV 101.33 kpa x (1.673 _
= 0.001) m3
= 169.4 kpa.m3 = 169.4 kN.m-2.m3
= 169.4kI
Then

ALI =2256.9 - 169.4=20g7.5kt f.+-^./t ) Q'J14)

 .-!.*.a.:.r i, -1-\'s{r vA:.', ll } ,1.. ,r ;.11:-t, JX,!- .'l -' ;' :rii' . -'-''^t .', N'tJ
11 1-,1 -t,..r'J.'.

) rL) ar),/,5- *':'(1"-L? 5.rLltL-;'.,-r:,'-.'1 u.l' rY-i ;.,!tj 1-, ,l- 4r.: .1.;,:.
:
, 4,., ),)
t';jtA.-t t,_))- )J-J U .= .-o ?, \, G L,., r €'.;, **.3 *.., / y' r ?+,]r €
4rU l'4eJpI L-l'-:L-p- --*r-" C *r+' t'\i <-'t('\-;-rrJI at),.e Zt1,,o-",*il,6t 4.
,4.)
CHAPTER 2. Tlte First Laut and Other Basic Corrcepts

2-a HEAT CAPACITY

ts! )l-"'+\;' q-rL-'J l -zp+s itr;':t''t' "t:t:J""t;
(-a>ty't: ,-
i' i" 6 "'t i '-)vj
'41 ji -,' -t t d' .4a;.,t', *- t;'-*
) gllt ;-"y-?t
2 1

Our lecognition of heat as energy in tr:ansit was pleceded historically by the idea that gases,
liquids, and solicis have capaci1, for heat. The smaller the temperature change caused in a t^
UU
substance by the transfer of a giveri qq
might be defined as C = dQ/d
c-- ' J+
process-deperident quantity lather than aSgl*Utggi-o,ll. Howevel, it does su-{gest the defini- ( ) t, ,.1 ., 14 l-a'.-L
-capacity
tion of two quantities that, although they retain this outmoded name, ale in fact state functions, 't
lrP , ;' , ," 'ttt ry|"
\

unambiguously related to other state functions. The discussion here is preliminary to mole
complete tl'eatment in Chapter'4. lr^.4;un Q u')a 6- '-' .z1f-t l
.'--"'." "l<
5+./r. t:'

'cjtj t'"''P"' u,!t -P t."

-l
Heot Capocity at Constont Volume t
The constant-volume heat caDacitv of a substance is defined as:

-'- (y\
c,=
\dr )u
e.i5)
Observe carefully the notation used here with the paltia_l dg1lvatrv-e. The parentheses and sub-
script Vindicate that the derivative is taken witl.r v-o,lume held constant; i.e.,L./is considered
a function of I and V. This notation is widely used in this text and more generally in ther-
modynamics. It is needed because ther:modynamic state functions; like U, can be written as
functions of differ:ent sets of independent variables. Thus, we can write UQ, V) and U(7, P).
Ordinarily in multivariable calculus, a set of independent valiables is unambiguous, and a par'-
tial derivative with r:espect to one variable implies constancy of the others. Because thermo-
dynamics leflects physical reality, one may deal with altelnative sets of independent var-iables,
introducing ambiguity unless the valiables being held constant ale explicitly specified.
The definition of Eq. (2. 15) accommodates both the Elat_beat gapacity and the speciflc
gqt glp_Try (usually called spgcific bg4t), depending on whethel U is the molar or:ip&iffi
-t
internal enelgy. Althoueh this definition inakes no leference
enelgv. Although ryfe51ge,.193ly
process, it lelates
to any plocejs_s, in an
lelate!_in
especially simple way to a:gI$4!E9brn9_LrTEs-s_ in a clo-sed system, for which Eq. (2.15)
may be written: C-<V.-* -t-\*
t)
^7r<or,\ilj
dU = Cv dT (const \4 (2.r6)
Integlation yields:
.7.
lU
- = JTt
| Cv dT (consr 14 (2.r7)
Iir-):{?ru
This lesult with Eq. (2.9-) for a mechanically_r'evql'sible, constant-volume process (condi-
tions that preclude stirring work) gives:
/., ,,\\A/ ..t
b> 1,+-l t ,/ fTz -. ._)
'-:l-:-1
j

O=LU= I'I CvdT (const V) (2.18)

J t, \r,: ._-.\
.'-1, I
r

If the volume varies during the process but returns at the end of the process to its ini-
tial value, the,pr,gcess caryglnglqy_bglall94 p!e_q!Sq'l!_!ent_y9lgqre, even though Vz=Vt
and AV = 0. However, changes in state_functions ar-e fixed by the initial and final conditions,
 2.8. Heat Capacitl'
43

o{.path, and may thelefore be calculated by equations

-independent for a truly consta't-volume
process r_egardless of rhe actual-,!Iqc_9ss. Equation
(2.17) ther.efor.e hass general validitv.
because U, Cv, T, and Vare all state functitgs
.r.L,,- rl:--76-Tr Qn 1tr9 other..hand, and F;n.6rd
C 4rru
."s^rY! Y: rr ucPsrr( oil;;.
ll,li: l!:
(2.TBI_ls a.valid expr-esiion ro,
volunte pyocess. This is rh
A uno W i. tn n"n".rr'ffi-#; for aioiffiir-
etween state functions aud
path-dependent quantities
te functions ar-e path- and
plocess-independent is an
iqr
For the carcuration of property chan!e's, but
not for Q and w, an actual
process may b'e replaced by any other
same change in state. The choice is ma
simplicity a great advantage. \ ,- /
w..,Q cAr ,eL+
Heotcapocitydtconstontrr"r"f, ,!'':Jl',WLT-J'r:&\ffJ,;:;
Theconstant-pr€ssureheatcapacityisdefinedas: '"6rs)r;)r---)t_-t,- *l!1
,,= (#), (2.r9)

t capacities, depending
in an especially simple
is equally well written:

dH = CpdT (constp) (2.20)

whence
'rT.'

^H= 1Ttf Cp dT (consr P) (2.2r)

a mechanicalry.reversible, constanGp process;.thie
_ ^lT + (.e--''- ,p)
r.esu)t rnay be combi'ed with
Eq. (2.12): .ol+ -- O
Q=Mt= [" (2.22)
JTI

" ^ - - rh
:,?,Sfi";
,;-P (r:1:
*
;:
pi ?
,,.1,t)4,ft
,,\
-4 l-
f;:-.."^
rea-
E^
:rT lT._.:^ nt, !?,?Dappties to unffir-ror. which pz.=
:':::j:::jil:?.:1ffiJX,t::;H:lfld,lffi@
.**ffi..".llTil'i;Jlllft"+aoi*iiffi'fffi
tc,r;. yz.zo1 ouu wurK uy Eq. (_r.J.l, nere
cess can the amount of heat transferEdJG'jdl
wr.itten for I mole, W = _i
AV.

Exampfe 2.7
Air at 1 bar and 2gg. 15 K is compressed to 3 bar
and 2gg.15 K by two different
closed$iiem m5lffiitty reversibte p,o.essds
(o) cooling at constant pressure followed by
heating at constant volume.
(b) Heating at constant volume followed by
cooling at constant pressure.
 .bu= q G.Qc bH = Cp AT Lro -b$ t*--s --,., i,i >:,,r U 'oE-s' t'z'
\M- - trrV c,-- W \-
" A1+: Au*N(evl 1.-- AU.-J\i
,.--_\:^_? r .2py,\_=, w Jq :, bd rqJ N\-:: ca bT t',-o NU i---" ::v "$ €
-
" aH--au-t A (ev_.) (* bll
-Jt
44 CHAPTER 2. Tlte First lau, and Other Basic .t

I
Calculate the heat and work requirements and AU and AH of the air for each path. The
following heat capacities for air may be assumed-indeilenOent of temperature:

Cv=20.-/85 and Cp=29.10OJmol-1'K-1 . -.,rI'\., I

' Assume alsothatair remains a gasforwhic h?Jrllisa constant,F#r#s;;rt;;ffi;rf1 ''r*

it undergoes. At 298.1 5 K and 1 bar the molar volume of air is OfiZ7-g m3, mol-1.

-_ 3\o*_- Vr r o,ott+1
2
at: _LJEtt \.
S,
of air contained in an imaginaly piston/
eJJes alemechanically reve$!]g {ggiqqolr
thout fi'iction. The final volume is:

/l\ - .',J
a*'y'
79f l)=0.008263
\J/
m3
P diaglam of and on the Zvs. P
Ip;,3JD

Figure 2.3: 7 T
o
vs. P and Ivs. F
P diagiams for E

Ex.2.7.

01230123
P bar P bar
(I) (ID

(a) During the filst step of this path, ail is cooled at the,co-nstantplessul€ of 1 bar until
the final volume of 0.008263 m3 is leached. The temperature of the air at the end of
this cooling step is:

T,=^,,
v2 -^^ --10.008263.)
,r= ze6.ti\ A}Z4.'g / =99.38K
'\_y' -,r nus, Ior tne llrst step,

O = L.H = Cp LT =(29.100)(99.38 - 298.15) =-5j841

W = -P AV = -l x 10s Pa x (0.008263 - 0.02479) m3 = 1653 J
AU = AH - L(Pt/) = LH - P LV = -5184* 1653 = -4131 J
 t

2.8. Heat Capaci6, 45

\4,
t rne secol'l. step rs at constant v2 with Jreati'g to the
for this step:
firal state. wor.k l4l: 0, and

AU = e = Cv AT = (20.].85) (298.15 _ 99.38)= +t: t I

' V Ap = 9.999263 m3 x (2 x 105) pa = 1653 J
LH - AU + A(pV) = LU + V Ap = 413l + 1653 5784 J
=
For: the over-all pr.ocess: _

Q= -5784-r 4131 = -1653 J

W=1653+0=1653J
AU =-41.31+4131 0
=
.5i8i,4+578|':o -+ >T = 7.:
.?| -i.rr.-'tu'-'
dH= 1 .it"
Notice that the first law, A U =e+ w, applied ro the overall process is satisfied.
(D) Twod oduce the same finai stare of the air. In the first
step ai me equal to yr untit tire fina prG$r.e of 3 bar is
. reache end of this ;iflis:
7' =r,P*=2e8.15f:) = 8s4.45K
rt \ r,/
@ fot this fir.st constant-volume step, I4l = 0, and

Q = AU - Cy AT = (20.785)(894:45 _ 298. 15)

= r2,394I
,

V AP = (0.02479) (2 x 105) = 4958 J

A,H = L,U * V AP = 12,394 + 4958 = \j,352 I
,"the airis cooled aL4_= 3 bar ro its final state:
second step
O
Q = AH - Cp LT = (29.10)(298.t5 _ 894.45) = _|j,352I
w = _p LV = _(3 x 105)(0.008263 _ 0.02479) 4958 J
=
AU = AH - L(PIa = A,H - P AV
= -17,352 * 495g = _12,394I
For the two steps combined,
-n)\z
'Q
= 12,394 - 11 ,352= -4958:Jj
-'"u " r."4tt) r'"<'|
w= 0 * 4958 = 4958, iy' '\,1
S-H +CT)
Lu =12,394 -i2,394 =0 6Z onr.
LH = ll ,f52 - 17,352 = 0 z;,y
"
 *

46 CHAPTER 2. The First Law and Other Basic Concepts

Example 2.8 o,,r Lir,

Calculate the internaf en"ergy anO enttra'tpy changes resulting if air changes from an ini-
tial state of 5oC and 1 O bar, where its molar volume is 2.312 x 1 0-3 m3.mol-1, to a flnal
state of-6,0"C. ald ,l !-ar. Assume also that air remains a gas for which PVlTis constant

":':l ='^'l"-',T5'J','Y1' E) -=rr', -"'- a u4' u \f,, " *"

:" 2.8
Solution :;' ' -J.l-x*" nt'

Because pr:ope ess, calc . \::. i 1 ,.'p, , ; 't . t

olr any process we choo
ically leversibl ) cooled
tJ-1' r' r,'+\ c ' t-' L ' o

the final plessule, and (b) heated at Constalt pressule to the final temperatule. Of q--j J ' -tr ' : ;
course, other paths could be chosen, and would yield the same t'esult '--a;* t
Zr=5+213.15=218.15K Tz = 60 + 213.15 = 333.15 K
With P7 = kI, the ratio 7P is constant for step (a). The intelmediate temperatule
between the two steps is thelefole:
-
.,,, ', . ' l:r .'1' :
T' = (278.15)(1/10) = 21 .82K t'.-a:vr5l ' No"'

and the temperature changes for the two steps ale:

ATo=)1.$2 -278.15 = -250.33 K
AT6=333'15 -27.82 = 305.33 K
AV: i c--..rJT ' '' 'i-
For step. (a), by Eqs. (2.17) and (2.14),
(y
.n
LUo = LTo = (20.785)(-250.33) = -5203.1 J

LHo=[(Jo+VLPa Ll-fo) -t:L*- t",)

= -52Q3.7 J + 2.312x 10-3 m3 (lS * t05) ea = -izgz9 I
"
For step (r), the final volume of the air is:
P'7. ^/10x333.15\
- 'Pztt
,V2=Vl#=2.31? v 1o-3I
\rxzzs.rs)-" "':,,'" 'l'.^,*
ByEqs.(2.21)and(2.]D, 1-]F:
l*u'
LHb = Cp LTy = (29.100) (305.33) = 8885.1 J -
AU6 - P AV1,
= trl1o
F" * -z
' tL/ '=''j' {'' '

= 8885.1 - (!!J95)(0j027.69 - L993])= 634't.r I

*i;"1..,. \JrJ/-
For the two steps together,
-5l
AU = -5203.1 + 6347.1 = 1144.0 I
LH = -'1283.9 + 8885.1 = 1601.2 J

These values would be the same for any plocess that results in the same change of stafe.S

SYou might be concerned that the path selected here goes through an intermediate state where, in reality, air
would noL be a gas, but would contlense. Paths for thermodynarnic calculatitrns oflen ploceed Llur.rugh such lrypothet-
icrl sl.atcs Lhal. cannoL bc physically rcalizcd but rc noncthclcss uscful and appropriatc for !hc calculation. Additional
such states will be encountered repeatedly in later chapters
 2.9. Mass an.d Energl, Bal.ancesfor Open Syslsnls 41

2.9 MASS AND ENERGY BALANCES FOR OPEN SYSTEMS

Although the focus of the preceding sections has been on closed systems, the concepts pre-
sented find far mole extensive application. Tigtgyq_g!_lq3ls *d
*btgy.""t"ryqti""
zJl processes, ggpgl -^q ed, the open system includes the closed
Tystem as a special case. is therefore devoted to the tleatment of
open systems and thus to the development of equations of wide practical applicatiiTl----

Meosures of Flow
Opeu systems ale chalacterized by flowing stl'eams; there ale four common measures of flow:

. Mass,flow-rate-n'r-.-Mqlsr' flq\tr'-14ts-1.i-.-Volumeh=ie-flow-Fa.te, q---Veloeitytu-

The measures of flow al'e inteil:elated:

rit = ,./hi and q=uA

where -,tt is molal mass and A is the c::oss-sectional alea for flow. Importantly, mass and molar
flow rates relate to velocity: gfi- L4 A
^. q
,a'=11 _0 ,v.,,, FL
'v't''.f*
Z_o

uAp (2.23d)l
tit=uAp i=uAp
n = uAp
u F,, I tit = (2.23d) | (2.23b)
(2.2Jb) | -'F;'J'q'*''
'?
\
The ar-ea for flow A is
,9,t*-n^ e,i yt
cific or molari/ " ' "

density. Although velocffis

(J---
te as the aver-
v )-'s)''
age speeT6ffitream in the L-'ri- \
sent measules
of q[-uantity per uriit of time. the ) t "o:u--"?'
ot suggest
magnitudeof flow.Nevertheiess,itisanimportantdesignparamete-r., r_7\_ t , , ) ^l'r?, ri <tn.".n,
, tEJ1'62*tT >rY t--')'

Example 2.9 t{tt c'!i"!'

| a/)'Pt'over
- t, .ln a major human artery with an internal diameter oj-S-nm, the flow of blood, averaged
,-*' t, the cardia.c-qlcle, is 5 cm3.s-1. The arlery bilurrglgs (sglits) into two identical ^
blood u.GEiiffi'F" each 3 mm in diameter. What:are t66-iverage velocity and '
the mass flow rate upstream and downstream of ,the bifurcation? The density of blood
is 1.06 g.cm-3. --\-*'-1
,a -j
Solution 2.9
The average velocity is given by the volumetric flow rate divided by the area for'
flow. Thus, upstream of the bifurcation, where the vessel diameter is 0.5 cm,

a -5 ''-':-
cm3.s-l
u,,^=L=(z/4)(0.52 ; =25.5cm.S-t
A cmz)
 48 CHAPTER 2. Tlrc Fit-st l^au, and Otlrcr Basic Cortcepts

Downstream of the bifurcation, the volumeh'ic flow rate in each vessel rs

.2a5 9rr{ s-1, and the vessel diameter is 0.3 cm. Thus,
2.5 cm3.s-l t\
&down = 35 4 cm's-r
Ol )O5-;e=
The mass flow late in the upst'eam vessel is given by the volumetr.ic flow r-ate
times the density:

tit ,= 5 cm3.s-l x 1.06 g.cm-3 = 5.30 g.s-l

Similarly, for each downstream vessel:

tildown = 2.5 cm3.s-3 X L06 g.cm-3 = 2.65 g.s-l

which is of course half the upstream value.

Moss Bolonce for Open Sysfems

The legion of space identified for analysis of open systems is called a control volu.nte; it is
separated from its surroundings by acontrol snface. The fluid withil the control volume is
the thelmodynamiclFlEm for==--r which mass?nd energy balances are writteu. Because mass is
conserved, the rate of change- of mass within the control volume, dn""/e, equals the net rate
gf lqry o:lgq s into the control vohime. The conventiol ti ttr-e!.4_o;ry is p&rliv.-r,." dii"._r-ga
rnalg-cg!!lgl volumg3ld.negative wheiltE_ct6o ouTTtre mass uutilffixpressed marh-
Jra -;, *v1
o-* + -v< v-
l,\. lf,{ t
c{ }'>
) -'s'l a!;i 4
c'rd, ('-
;,+A(r?x)rs // &rl- ^'''.t
D -.t t;"j
(2'24)

5r,r,, -'--"+u?'!(,-i'""
{*iiiJ
For the control volume of Fig.2.4, the second term is:
:: z:. ( lowr*9 5 1,,rsu,..,....s
9,t 1l ''' ^rtl"r-! o,@t Js,J t+A(r'z)p,= th3-ity-rit2

,.\-
Figure 2.4: Schernatic representation of
a control volume. It is separated from its
Control volume
surroundings by an extensible control
FJ\ :{,\,r J 1* dnt"r/dl
surface. Two slreams with flow rates ni1
and th2 ue shown directed into the conirol
volurne, and one stream with flow rate ztr
is directed out.
Control surface
--a
 Mass and Energl' Balatlces for Open S.

(2'24) becomes:
When the mass flow late ni is given by Eq' (2'23a),Eq'

e-first-svaeeurn

Because specific volume is the recipriccal ofdensitl' / = l.

. utAt=-v,
ry=-vt
uzA2 uA
=n (2.26)

This folm of the continuity equation finds fJeLuent use'

/'- \r -.
te-,i4,\---?\.u\ ";r-i.;-r1t
t.t

Energy Botonc6
e*r r ,F b2*- ;7w -ut- +t IfJa
The Generst "
,'
ate of change of enelgy w8rln-,tfle control volume
il C-on6l volume. S-tt=u*i flowing iuto and out of
-e-nagy
in i potential, and kinetic forms'
L
I

rtit mass of a stt'eam carlies

i average velocity of the stream' z is its eleva-
I
tion of gravity. Thus, each stream tl'ansports
i!.lo thg rlstem bY the flow-
I

of the minus sign with "A" is

I
rccumulation within the contlol volume
x
tateQandwortrate: - l>
I

I -*Tur-bd
-t)J''
!+.
a
7- -/
6- d(rn?"'
dt -a [(ur+
u*,i* * u),rf
=
,r,j,
*0+workrate
,,
-r
t
 50 CHAPTER 2. The First law and Other Basic C,

Figure 2,5:
Control volume
with one entrance
and one exit.

,, Ut Ht"-- u, ,

.,^ o ^""-:ll\["' ted with moling

tne lowlng strcams or exit hii i-set
of avelage properties these prcperfies
:l::i::'"ii:ll'i1":
additional fluid, repraceo
here. Dy a prston that exerts the constant pressure p. The wort
done
s acted upon bv

.ptnt-s-l, ts,qe,lil
-:1:111v. +Y:lilf ry1n.]i,ll"! yult
1iYljg.,..a^: Elit t_rlztss-tln9lgn
ry:S_gglglt4" rne enll'allce ls_ly, and the
qlt'_q't.e !-s_p_v,
secause a denotes lhe dltterence between exit and entrance quantities.
workffiis
rhe wor.k r.ate is (PIz) I7x. (ii4;.
the.pet work donE oz
the system when all enh-ance a'd exit sections are taken into account
Anothel form of work is the shaft wor.k9 indicarec in Fig. 2.5 by rate Iizr.
is -aiiFr4ral rs. 4--
In addition,
work may be associated with expansion or contraction
forms of wort are all includedli?lffit"r*i*.iJlJ
now be written:

d(ruUc, l/ I \ I
--f =_ol(u+ru2+zg)nl
L\ Jrs
+
..> na qy b< sfiyt' j*J i,Jor k
combination of terms in accor:d with the definition of enthalpy, H U
= +p /, leads to:

dtutA,, l/ r \ r
dr = -o |
L\
(H +
_4u2
+ zg)nl
/ lfs
=e+w
..P s:i , t )-, 7:t..7-), .l
)l
46x"'5:H#'-r i'" (t ''
&14rtu4\*v:-P:^) (, .i* + ,),2 = g+w (2.27)

m :_ f*a The velocity u in the kinetic-energy terms is the bulk-mean velocity

as defined by the
equation ,=lq4) Fluids flowing in pipes exhibit a velocity profile th* rises fiom
zero at
9Mechani roved from the system without transfer of mass js called shaft
work because it is
ing shaft, like that in a turbllg or compressor. However, rhis term
:lt"n,,ttuntf"
rn
oroaory to y olher mechanical means as well.
rs used more
 2.9. Mass and Drcrgy Balances for Open Systems 51

the wall ( at the center of the pipe. The kinetic enelgy of

Ti[id-uidin u the case of laminar' flow, the profile is Pat'1-
for u' k t
I avkts
bolic, and integlation acticss the pipe shows that the kinetic-enel€y term should ploperly be u!.'
In fully developed tur-bulent flow, the more common case in plactice-, the velocity across the
major poltion of the pipe ir ng. and the expression u217, as used irr the
"l"tQY , _.
is
"gtr "g!ql",
m-qre-Leady-ggqgt --+ F E hqrbq\carF 'Flow
",
"quations, is an energy balance of t:ry!]99!eEliry, it has limitations.
Atthough Eq. (2.27)
Iu par.ticular', it leflects the tag[ :ssgllption that the center of mass of the contol voiume is
stationary. Thus no telms foiEnetic- and potential-energy changes of the fluid in the coDtlol
volume are included. Fol virtually all applications of intaest to chemical engiueers, Eq. (2'21)
ri'-r is adequate. For many (but not all) applications, kinetic- and potential-energy changes in the
flowing'streams are also negligible, and Eq. (227)then simplifies-to:
(d!-,/ #; 'S ot4}st,
I

d(nt()",

Flou/lng tz Ftt YE'":"\'L)\|t'-:l

9,t-re+s5

Example 2.1O
Show that Eq: (2.28) reduces to Eq. (2.3) for the case of a 9!egeq-systell
\t au+=
e +.r.1
Solution 2.1O
The secong ter{.i of Eq. {2.28),is omitted in the absence of flowing streams:

Dft?)r)- " !9#=s+w

Integration over time gives
fI2 rl1
I
L(nrU)", Odr +|
L
" tl
Jtl

*, L;*<"-
AUt= QIW'-
The Q and I{ terms are defined by the integrals of the pleceding equation.
Note here that A indicates a change over time. not frotn an inlet to an outlet. '
g One must be awate of its context to dis-cqp!!9-494414g' :-
\gV*o rz { -
n 4' \t'J1 z-z-a -"
"
b *-

Exa mple 2.1 1 ftl

An insulated, electrically heated tank for hot water contains 190 kg of liquid water
at 6OoC. lmagine you are taking a t-qwe_r using water from this tank when a power
. ,.s .lgit e- outage occurs. lf water is withdrawn trom tne tank at a steady rate of rh = 0.2 kg's-l'
}Y,L
3\{<,
-t):-l
 52 CHAPTER 2. 7-lte First l-au, and Other Basic Cortcents

J1
2'11 Pa --o !'o)'
, ..n)?rLl .rsolution oi|: -ur9)<+)1
This is an example of the application of Eq. (2.28) ro a rransien6rocess for
'j*':; , )y/ which
a\ -/
r.>' ' ,92
-7 " ,92 Q = W = 0. Wr assutre perfect
rrerfect mixing the conrenGAIE;i;;F
mixins of rhe contenFFrhe this i-^r."
tank; thic
the rante. imrrlies
,, t'l;u'u"
r..lr l'1 r,L''
" ,N
)',''u/ ,t'''7'
du . == ,,, KE-- Ptsz o (? ,z &)__
mV*ir(H-H)=0 ^ F
wheLe unsubscripted quantities refer to the contents
fla\ = 4ewlr*''l:
of the tank (and therefore the
watel leaving the tank) and F11 is the specific enthalpy of tbe water entering the
tank. With Cv = Cr - C,
, .,c r.a.)
J0-c,.J-
tJ--1-
dU
_-=C: ^dT and H-Hr = C(T-T)
4- c./ A - (""\-r
dt dt
o.
t''- --' Q'-
-J-
The energy balance then becomes, on l.ear.rangement,
?"-"^l
- d-- -f .r,r, c (T- \ ) : o Ui+e /',
- dr
'{ dt = -'"it . T-T1 i:-- 6 o'< v-

Integlation from I = 0 (where T = Td to arbitr.ary time t yields:

t= -t!ht(=\ To = (o"(
uL \10 - I l,/
Substitution ofnumerical values into this equation gives, for the conditions ofthrs
problem,

,=-36fi:-l9\ =658.5s
0.2"'\60-10/-""
Thus, the water temperature in the tank will drop from 60 to 35.c after about
11 minutes.

Energy Bolonces forg@-_S-!Se FIow processes

Flow processes for which the accumulation term otfu. (2.27), dQn(t)"uldt,is zero ar.e
said to
occur at steady state. As discussed with respect to the mass balance, this means that
the mass

t -, ^ ,\ d ( n rJ)-Y
+ Af
( i.t -r -i,,,' -, z t) *1^
- It
>q +^tr
\L-t'r-tl=> dt
 /\' ,Sot' Vtl,rst/ -f' ^,15' >' /o
-, q.2(("atia
54aly s[J.+dp =-
5.({i,-1:'x*1'^fi ,

.U,ltr6,rJt-Q v,'&\
2.9. Mass and Energy Balances for Open S)'stents 53

an-{es occur lvith

ces and exits. No
olly wor-k of the

o'ryy--'
Q+Ws (2.29)

@ t+, &?*l:.2, :r,

t\ ]**u),r],"
I ^[(". z / I = is

. \ -.i31)fr,','nrrrrough "steady state" does not necessarily i.ply'g4g" the usual.application of

\.t.,
this equatioili-to steady-state, steady-flow processeslbecause such prrccesses leplesettt the
>41 industrial nolm.lo
A furlher specialization results when the control volume-has ope enlgAnce and orre exit.
The same mass flow rate t?i theD applies to both streams, and Eq. (2.29) reduces to:

,p!-o\r- u
r\n
a(a+
\
|u2+z.glfi=Q+w,
L t->
(2.30)

where subscript "fs" has been ornitted in this sirnple case and A denotes the change frotn
entrance to exit. Division by rl'r gives:

\ Z -/ =9*\=g*w,
t(n+1,'*.r) t1x In

L.u2
LH+ , l-gLz.=Q*w, g q ,?'-!'r= e.3r)
This equation is the mathematical expression of the first law for a steady-state, steady-flow
pro."$ b"t*.en one entrance and onqgxit. All telms represent of fluid.
"a.tgl!.t]t!.uss
The energy unit is usually the joule.
In many applications,ffic- and potential-energy terms are omitted because they are
negligible compared with other ter
?ftc.ss
F.S -- PG --e
This
for a
modynamic property of importance, and A refers to a change from;Dl9!.jg!9!, rather than
- rJ. t-- _sv
rr\ . ?^*t!r*" J 0 )i au H)\'z'lz) jt)
t
--1','
- ,rli* )),
Itvt\,r -
ul;at 'J:--'3 5)\ (z' ')t@ u2 tg'

,tdVl ess that is not steady flow is a water heater. in which variations in flow rate are
rate of hear transfer, so that temperatures throughout remain constant.
( i^,]i
llNotable exceprions include applications to noz4gs, metering devices, wind,tur,ll:\,and hydroelectric power
stations. n?t ?"t'^'t;' '
".t\

oFt'
i
 , ( 2-Jr 2 z, s"' \' n1*-,i ':1

('(rJ:a.L CavJtl'ia'ns ) +**\ <-ep,, t;V\ ,'), d ] i-' <]

), ,u-3 G
-Sn',Iol"virn/o') aylt-p-" t7
1,.-) lz-'"au,L-',rit..'a 2,6 "-#
t(1;' ({)
54 CHAPTER 2. The First lnw and Other Basic Concepts
l r.)

A Ftow cotorimeterror Enthotpy rvr.oJf.;-;;';"tt

tt "SiTi:;; K'; llfA- g,
TheapplicationofEqs.(2.31)and (2,32)tothesolutionofpracticalprobiemslequiresenthalpy t"-1 t*)uot\'

; Ut, ;d_-1 s,t l;t Qt

z4a- ltle2 -o., 1'+ t

'-r-e
ts i "t-* .fi,

-^tl)'t.U tL\-l Jzf',: .

t itt b4t )\ (5'
e-a!-t ) ,Qy ..tJ', '
,r -J t ll rinl .,: ri;r
))\tuy'ot=-t'"^t (.,r:,-.,'''.:--- 6V
a=o'( {l
' A simple flow calorimeter is illustrated schematically inFig.2.6.Its essential feature
immelsed in a flowing fluid. The design provides for minimal
'-! rz '-- 't z from section-l_ to section 2, making kinetic- and potentialen-dfr
f A, changes of the fluid negligible. With no shaft work entering the system, Eq. (2.32) reduces to
" AH = Hz - Hr Q. The rate of heat tr:ansfer to the fluid is determined from the resistance of
th_e.hgater and the cut'rent passing tlu'ough it. In practice a number of details require car.eful
aftetrtion, but in principle the opelation of the flow calorimeter is simple. Measurements of the
heat transfer rate and flow rate allow calculation of the change A,F/
letween sections I gnd ?.
Fol example, enthalpies of both liquid and vapol H2O ar-e readily determined. The
constant-temperature bath.is filled with a mixture of clushed ice and watel'to maintain a tem-
peratule of OoC. Liquid water is supplied to the appar"tus, and the coil that carries it thr.ough
the constant-temperature bath is long enough to bring it to an exit tempelature of essentially
0'C. The temperature and pressrie at s-6cti6i 2 are measured by suitable i-nstruments. Values
of the enthalpy ofH2O for various conditions at section 2 are given by:
r,'l U' -f\r= G
-
Hz = HtrQ
where B is the heat added per unit mass of water flowing.
The pressule may.vary ftom run to run, but in the range encountered here it has a neg-
ligible effect on the enthalpy of the entering water, and for plactical purposes .F/1 is a con-
stant. Absolute values of enthalpy, like absolute values of internal energy, are unknown. An
arbitrary value rnay therefore be assigned to Hl as the basis for all other enthalpy values.
Sefting llt = 0 for liquid water at 0'C makes:

Hz=Ht*Q=0+Q=Q
-^L I Y " I Y - Y , . / /'.\
*'.'
/u'L./o).1't'-,:'-aii y'\,';
/], \.,./ .i -,i,,/,-./,
- !. -r r (2)
-, t.tt -o^r,+t:l 1t lazP" ]cr'!' :)
. -nn_ vn /o).r, d.ou\ .v "/,l ,-.
(J)d.rt.ty' (l
,

/ , or_
.'1
, *"_ ,,n ,:eo(_ @
ur_,*
L.t\f i,,<r:' y -u ,
,r - ) ()/^
.:-
147=)At *Q ,- '?iru,o-Y,*'(:&7"-"i"g, "Li,a "
^,

L-/ tu'** r' i ' .7;,'*',,' I,),i,,-,;t' ":i ".' .e.9

2; :;:7:,,,Jt.
d,''Y" :u' --,t a:;',': ?1; P
'-j)-t-+t V
-u ."-,Vir ,/t' r $- u*, i,r-stu\ rtu'G
.,
,V,.r,);t,) 1_= ooc p S rJ)rrAr 14,=o ,uN u? e--kst 2^p4 bas,s -f .^+zg4tet)d @
l-fz-tQ 2-f) c'ulJ o 3l @
-, .rtt}
,-F ifu.-rg ,try{. ,--s A* v )";.ilt,
(v)"// #' e 4:rJ+p,/ .J:v v U "$bJi'&Wt u'+ sil,
tcv,r'i & -o"u#- d
-)).,j,9-:J+ir &,,j)t,--'-
UaH-Pv 55
2.9. Mass and Balances for Open S.

,r \ll ry?f dty'r':'"1' *

Enthalpy values may be tabulated for th-e_tegperq!:gles and pl'essures existing at sectioll
Z foL ilarFnllqrlgr CIlus. Iu addition, specific-volume measurements made for these same
;;aiti"";iy tbe-table, along with corlesponding vaiues of the inte::nal enelgy
be_ad=d_ed_tp
calculated by Eq. (2.10), U = H PV. In this way' tables of thelmodynqmlgIlopgEies-al'e
-
compiled over the entire useful range of c6nditions. The most widely used such tabulation is

,rd

,\-.el-
,?7 Flow rate = 4. 15 g.S-1 tt = OoC fZ = 3OO.C PZ=3bar
' Rate of heat addition from resistance heater = 12,740 W -> d

The water is completely vaporized in the process, Calculate the enthalpy of steam .t'tt $ ),/d\
3Oo"C and 3 bar based on!-= 9 for liquid water at ooC. f* = tr a-FT= o
"c--,r-/. t+t';ri v
Solution 2.12
If Aj and bil are r.Egllglle and if IV'

9l<a- )oLl4 ry r? 740 r.s-r

9*?erh,,/"/ i!<et )\ ":!
'r=ffi
= :oz
v=3o€a,av4l9 e ""'- ^ "

Example 2.13
Air at 1 bar and 25"C enters a compressor at low velocity, discharges at 3 bar' and
nottle in which it expands to a final velocity of 600 m.s-1 at the iriiiiE-al condi-
"nt"oE
tions of pressure and temperature. lf the work of compression is 240 kJ per kilogram
of air, how much heat must be lemoved during compression? { '4 Jn

l2Steam tables adequate for many purposes are given in Appendix E. Tbe Chemistry WebBook of NIST includes
a fluid properties calculator with which one can generate tables for water and some 75 other substances: http://
webbook.nist.gov/chemisry/fl uic
 56 CHAPTER 2. Tlte Firsr Inw and Other Basic Cortcepts

3 bar .-_-z 1bar,25'C

Ws= 24O kJ.kg-f
a-l

ra?Z)+ :a- ?'

-t
1 bar,25'C

Sotution 2.13
Because rhe ail.r.etuns to its initial conditions of I
duces no cirangffi enlhufpy oi tt," ui. Mor.eover,

0= Q+ws

Then
..2
Q=?-w,
The kinetic-energy term is ev4-gatgd as follows:

I " 1/ m\2 m2 ^z L-
,u; = r(60o=/ = 180,000? = tso,000*'
rs5
= 180,000 N.m.kg-t = 180 kJ.kg-l
Then

0'= 180 - 240 = -60 kJ.kg-r -vc R_w1'o'rrtl

Heat in the amount of.€0.hl-must be-removed per kilogram of
air compressed.

Example 2.14 :
'* " ," ..r/ 2' "
at
water
supplies
r".a. p- heat at a
\ov'
5 t'f ,,
c'r aOOVe tn
ln\.!"',. !r,.

!,5" solu
This is a steady-state, steady-flow process for which Eq. (2.3
I ) applies. The jnitid
and final velocities of water in rhe srorage ranks are negrigibre,
uii n" rciiT,pn
 1'
w &t 1o'C =>5ai' ii1 (p,(gt):)speciA(!o\**<r t,o3 6"^-,3I i-
L
\3
f*l-n ^* looc :: iil -= o, tasz lJ
2.9. Mass and Energy Bal,ances for Open S),stems 5'7

may be omitted. All lemaining terms arc expressed in units of kJ.kg-j. Ar 90.C
- ---
"'t q o"|1,;
the denlilLof watei is
9.965 I(g._L-l and the mass flow rate is:
)t' nt')\P, y')O e> /?i = (3)(0.965)= 2.895 kg,s:r
r't -- f t", a
*=u-e
n - l*

For the heat exchangeq

e = _670t2.8e: = _231.4 \l\a_r

For the shaft wort of the pump,

w, = 7.5 /2.895 = 0.52939-r

Ifg is taken as the standard value of9.8 m.s-2, the potential-enelgy tem is:

P b+ gAz = (9.8) (15) = 147 m2's-2

= 747 J.kg-t = 0.141 kJ.kg-t
- ,.^\'1
Equation(2.31)nowyields: :) srr +f r- 1b7= 'r-Q+U:

;.tN'tyPt r?, e- AH - Q+Ws- gLz = -231.4+052- 0.15 = -231.03 kJ.kg-r

The steam-table value for rhe enthalpy of liquid water. at 90.C is: c g+<q
"/ E ! t 5.,:luro,&.1
F 8

Ht=3't6.9kJ'kg-r 'l=9noc:) t- -J2<.: q/tg

Thus,

AH = Hz- HL = H2- 376.9 = -231.0

and

Hz= 376.9 -231.0 = 745.9 kJ.kg-t

 !.. @
/21
?\'u" , )rd.\r!
I c.) )P

r = 34.83oC
In this example, lV" and gLzare small compaled with Q, and for practical purposes
could be neglected.
. , /re\^rJ fl. fl a" <-.\. e ) g ir ic ,F
'?E i'1t? a"'ru'e
)
-r'-

Example 2.15 ,l' 6/t

A steam turbine operates a!jgqq!!!!y with a power output of 49!_!W Steam enters
thg tlrb11g_a!2100 kPa and_475"C. The e,xlElst is satura_lgd +am at ]! kPa thqt
, enters a condenser. where it is condensed and cooled to 30'C. What is the mass flow
rate of the-stEam, and at what ra-tg must q_q9l!1g-water Oe3IEElieO to the condenser, if
the water ilnteE at 15oC and is heated to 25"C?

Solution 2.15
The enthalpies of enteling and.exiting stear! from the turbine ale found fiom the
steamtable^s: solnq-l..tl JLr*
€qg- :olut'l'
r,roi
g,.t.g<-zran^-lJ) .2 F'o^ ?q'e al \:'r'^i'\t'it'1
P= b ttF" )
p aLt6o\Lp^ jitr =34ll.3kJ'kg-r and Hz=2584.8kJ kg-r
L=l*/h Fol a properly designed tur-bine, kinetic- and potential-energy changes are
bl8 negtigiUte, anafor:aallUaticoperition Q=0.Eq.(2.32)becomessimply Ws: AH.

1M
-4000 kJ.s-r
,,rsteam
- AN7' = 4.840 kg's-j
^ (2s84.8 - 34r1.3) kJ.kg-t

For the condenser, the steam condensate lgyllg_is subcooled watel at

$, tor
which (from the steam tables) H3 = 125.7 kJ.kg-t. For the cooling watei enterrng
at-15-'iandr"uffi@c,itreintrratpiesid-.J dj f,no^ p,/gs
-)T=ja'c --:4,1!.:p.i"i4,'
eJ \i1, u f= ts'c t*?Hin= 62.9 kJ.kg-l and
l-'1-J Equation (2.29)here1edo..r-t_o0.6.,, gi\ <'T=z€'t :e ( .'i',. 5<Per'hr"lJ
. , (r . ,,^f .\r
t-r-*{r I "'lrst"a
t't iJ,'l'
H;)-+ ix*o* (Hout - Hin) = 0
^(Hl -
4.840(125.7 - 2584.8) + ri*ut", ( 104.8 - 62.9) = 0
Solution gives,

r??warer = 284.1 kg's-t

(?\
(1)
{{vT=3o"c
' S L.L26"l,al'vsJx r
2. 1 1. Probl.ents s9

2.10 SYNOPSIS

After: studying this chapter, including the end-of-chapter p::oblems, orre should be able to:

. state and apply the first law of thermodynamics, making use of the appropr.iate sign
conventlons
. Explain and employ the concepts of ir.rternal energy, enthalpy, state function, equilib-
lium, and revelsible process
' Explain the differerrces between state functions and path-dependent quantities such as
heat and work
. Calculate changes iD state v4r'iables for' a real process by substituting a hypothetical
r.ever:siblepl.ocesscotrnectirtgthesameStates
Relate changes in the intelnal energy and enthalpy of a substance to chairges in temper.-
aturc, with calculations based on the appr.opriate heat capacity
Construct and apply mass and energy balances for. open systems

2.11 PROBLEMS

,.2'1. A nonconducting container filled with 25 kg of water at 20'C is fitted with a stitrer,
which is made to turn by gravity acting on a weight of rhass 35 kg. The weight falls
s)owly tluough a distance of 5 m in driving the stirrer'. Assuming that a1l work dole
on the weight is transferred to the water and that the local accelerarion of gravity is
9.8 m.s-2, determine:

(a) The amount of wolk done on the water.

(D) The internal energy change ofthe water.
(c) The final temperatule of the water, fol which Cp = 4. 18 kl.kg-l.oc-l .
(d) The amount of heat that must be removed from the water to leturn it to its initial
tempefatule.
(e) The total enelgy change of the uuiverse because of (1) the process of lowering
the weight, (2) the process ofcooling the water back to its initial temperature, and
(3) boch processes together.

2.2. Rework Prob. 2.1 for an insulated container that changes in temperature along with the
water and has a heat capacity equivalent to 5 kg of water. work the ploblem with:

(a) The water and container as the system. (&) The water alone as the system.

2.3. An egg, initially at rest, is dropped onto a concrete surface and breaks. with the egg
treated as the system,

(c) What is the sign of I4l?

(b) Wlrat is the sign of AEp?
60 CHAPTER 2. The First Inw artd Otlter Basic Concepts

(c) What is AE6?

(d) What is A tr?
(e) What is the sign of Q?

In modeling this process, assume the passage of sufficient time for the broken egg to
return to its initial temperature. What is the origin of the heat transfer of part (e)?

2.4. Anelecticmotorundersteadyloaddraws9.Tampelesatll0volts,delivelingi.25(hp)
of mechanical energy. What is the rate of heat transfer fi'om the motor, in kW?

2.5. An electr-ic hand mixel draws 1.5 amperes at 110 volts. Itis used to mix I kg of cookie .?
dough for 5 minutes. Aftel mixing, the temperature of the cookie dough is found to
have increased by 5"C. If the heat capacity of the dough is 4.2 kJ.kg-l.K-1, what flac-
tion of the electrical_e_nergy_UlSq_lylhg 44_el__is_!9nu:{gq_!q inteI,gl-e19_lgy_9! lhg
dough? Discuss the fate of the lemaiuder of the energy.

2.6, One mole of gas in a closed system ur.rdergoes a four-step thelmodynamic cycle. Use
the data given in the following table to detelmine numerical values for the missing
quantities indicated by question malks.

Step AUIT QlJ W/J

,|

-'v12
23
-200
?
-6000
-3800 ?
34 ? -800 300
,| ,|
41 4700

,|
1234r ? - i400

2.7. Comment on the feasibility of cooling your kitchen in the summer by opening the door
to the electrically powered reifi'igerator.

u,'2.8. A tank containing20kg of water at20oC is fitted with a stirlel that delivers work to
the water at the rate of 0.25 kW How long does it take fol the temperature of the water
to rise to 30"C if no heat is lost from the water? For water, Cp = 4.18 kJ.kg-l.oC-I.

2.9. Heat in the amount of 7.5 kJ is added to a closed system while its intelnal energy
decreases by 12 kJ. How much energy is tansfelred as wolk? For a process causing
the same change of state but for which the wolk is zero, how much heat is tlansfelred?

2.10. A steel casting weighing 2 kg has an initial temperaturc of 500'C; 40 kg of water ini-
tially at 25'C is contained in a perfectly insulated steel tank weighing 5 kg. The cast-
ing is immersed in the water and the system is allowed to come to equiliblium. What
is its final temperature? Ignore the effects of expansion or contraction, and assume
constant specific heats of 4.18 kJ.kg-t.6-l for water and 0.50 kJ.kg-t.6-t for steel.
 2.1 l. Problents 6l

2.11.. An incompressible fluid (p = constant) is contained in an insulated cylinder

fitted
with a flictionless piston. Can ener:gy as wolk be transferr.ed to the fluidi What is rhe
\' change in internal energy of the fluid when the pressure is increased from p; to p1?

2,12. One kg of liquid warel ar 25'C, for which Cp = 4. I 8 kJ.kg-l.oC- | .

(a) Exper-iences a ten.tperature increase of I K. What is AU. in kI?

(D) Experiences a change in elevation 42, The change in potential energy AEp
is the
same as AU for part (a). What is Az, in meters?
' (c) Is accelerated fi'om'est to final velocity a. The change in kineric energy AEx is
-il the sarne as A [/ for.part (a). What is r, in m.s-t?

Compare and discuss the r.esults of the ttu.ee preceding parts.

--J;l3. Aa-electricanotomuns "hot"-underload;owinyointernalinwersib-ilitier. It has beeu

suggested that the associated energy loss be minimized by ther:mally insulating the
motor casing. Comment critically on this suggestion.

2'14. A hydrotur-bine operates with a head of 50 m of water. Inlet and outler conduirs are
2 m in diameter. Estimate the mechanical power developed by the turbine for.an
outlet
velociry of 5 m.s-r.

a-2.15. A wind turbine with a rotor diameter of 40 m produces 90 kW of electrical power when
the wind speed is 8 m.s-I. The density of air impinging on rhe turbine isl.2 kg.n-3.
What fraction of the kinetic energy of the wind impinging on the turbine is converted
to electrical energy?

'
,?:16 The battery in a laptop computer supplies 11.1 v and has a capaciry of 56 w.h. In
ordinaly use, it is discharged after 4 houls. What is the average iurrent drawn by the
laptop, and what is the average rate of heat dissipation tiom it? You may assume thar
the temperature of the computer remains constant.

2.17. Suppose that the laptop of Prob. 2. l6 is placed in an insulating br.iefcase with a fully
charged battery, but it does not go into "sleep" mode, and the battery discharges as
if
the laptop wele in use. If no heat leaves the br:iefcase, the heat capacity of the brief-
case itself is negligible,.and the laptop has a mass of 2.3 kg und an uulr.age specifit
heat ol'0.8 kJ'kg-t'"6-1, estimate the temperature of the laptop after rhe batrery has
fully discharged.

2.18. In addition to heat and wolk flows, enelgy can be transferred as light, as in a photo_
voltaic device (solar cell). The eneryy content of light depends on both its. waveiength
(color) and its intensity. When suntight impinges on a solar ceil, some is reflected,
some is absorbed and converted to electrical wor-k, and some is absor-bed and con-
an array of solar cells with an ar.ea of 3 m2. The power of
it is 1 kW.m-2. The array converts lTVo of theincident power
reflects 20Vo of the incident light. At steady state, what is the
rate of heat removal fi-om the solar- cell array?
 CHAPTER 2. The First Inw and Other Basic

scale) of
Liquidwater at i80'C and 1002.7 kPa has an internal energy (on an albitrary
t/,2.19. roi.o t<-t'tg-r and a specific volume of 1'128 cm3'g-l'

(a) What is its enthalPY?

(b) The water is brought to the vapor state at 300oC and 1500 kPa, where its inter:nal
energy is 278a,ald'kg-l and its specific volume is i69'7 t*3'g-t'
Calculate AU
and AH for the process.

t 2.20. A solid body at initial temperature T0 is immersed in a bath of water at

initial tempe::-
ature I,,4. tieat is tr:ansferi'ed flom the solid to the water at a t'ate Q=
K'(Tr,,-T),
of the
;her-e K is a constant and f,,, and T are instan.taneors values of the temperatures
fol function of time r. Check youl result
I water. and solid. Develop an expression T as a
, Ignole effects of expansion or contraction, and
for the limitilg .ur"r, = 0 and = oo.
"
speeifie-heats-foFboth watet'and sslid-
-assume-eonstant
2.21. Alist of common unit operations follows:
(a) Singie-pipe heat exchanger
(b) Double-pipe heat exchanger
(c) Pump
@ Gas compressor
(e) Gas turbine
U) Thlottle valve
(o\ Nozzle

for
Develop a simplified folm of the genelal steady-state energy balance appropriate
- each operation. State car-efully, and justify, any assumptions
you make'

the intensity of a
2.22. TheReynolds number Re is a dimensionless gloup that characterizes
For Re, flow is turbulent; for small Re, it is latninar'. For pipe flow, Re =
flow. large a
upDlp, where D is pipe diameter and p is dynamic viscosity'

(a)ItDand4arefixed,whatistheeffectofincreasingmassflowratezlonRe?
(b) lf rh and p arc fixed' what is the effect of increasing D on Re?

a conduit of circular'
2.23. Anincompressible (p = constant) liquid flows steadily thlough
cross-section and incr.easing diametei. At location l, the diameter is 2.5 cm and the
velocity is 2 rr's-1; ad location 2, the diameter is 5 cm'
I

(a) What is the velocitY at location 2?

(b) what is the kinetic-energy change (J.ks-l) of the fluid between locations
I and2?

by combining
2.24. A,stream of warm water is produced in a steady-flow mixing process
1.0 kg.s-l of cool water *;5"C with 0.8 kg's-l of hot water at 75"C. During mixing'
the surroundings at the rale of 30 kJ.s-I. What is the tempelature of the
heat is lost to
warm water stream? Assumeihe specific heat of water: is colstant at 4.18 kJ'kg-l'K-I'
 2.1I. Problems 63

2.25. Gas is bled fi'om a tank. Neglecting heat transfel between the gas aird the tank, shorv
that mass and enelgy balances prcduce the diffeiential equation:

dU dnt
H'-U n1

Hele, U and n refer to the gas lemaining in the tank; ltl' is the specific enthaipy of the
gas leaving tbe tank. Under what conditions can one assume H' = H?

2.26. Water 28"C flows in a stryight hor:izontal pipe in which there is no exchange of
^t
either heat or work with the surroundings. Its velocity.is i4 rn-s-l in. a pipe with
an internal diametel of 2.5 cm until it flows into a section where the pipe diameter'
abruptly increases. What is the tenipelature change of the water if the downstleam
diameter is 3.8 cm? If it is 7.5 cm? What is the maximum ture change for an
enlargement in the pipe?

(50) kmol pel hour of air is comprcssed from Pt = l.2bar to P2 = 6.0 bal in a
a.2.27. Fifty
steady-flow complessor'. Delivered mechanical power is 98.8 kW. Temperatur:es and
velocities ale:

Ir =300K Tz=520K
ul = 10 m's-l az = 3.5 m's-l
Estimate the rate of heat transfel from the complessor'. Assume for air: that Cp = In
and that enthalpy is independent of pressure.

2.28. Nitr-ogen flows at steady state ttu'ough a horizontal, insulated pipe with inside diam-
eter of 1.5(in). A plessule drop results from flow through a paltially opened valve.
Just upstream fi'om the valve the pressure is 100(psia), the tempelature is 120("F), and
the average velocity is 20(ft).s-1. If the plessure just downstream from the valve is
20(psia), what is the temperatule? Assume for air that PV/T 1s constant, Cv = 612)R,
and Cp - (7/2)R. (Values for R, the ideal gas constant, are given in App. A.)

/.2.29, Air flows at steady state ttl-ough a holizontal, insulated pipe with inside diameter
of 4 cm. A pressure drop results from flow through a partially opened valve. Just
upstream fi'om the valve, the pressule is 7 bar', the temperature is 45'C, and the aver-
age velocity is 20 in.s-|. If the pressule just downstream fior4 the valve is 1.3 bar,
what is the temperature? Assume for aI that PV/ Z is constant, Cy = (512)R, and Cp =
(7/2)R. (Values fol R, the ideal gas constant, ar-e given in App. A.)

2.30. Water flows ttuough a horizontal coil heated from the outside by high-temperature
flue gases. As it passes through the coil, the water changes state from liquid at 200 kPa
and 80'C to vapor at 100 kPa and 125"C. Its entering velocity is 3 m.s-l and its exit
velocity is 200 rn.s-r. Determine the heat tlansferrbd through the coil per unit mass of
water. Enthalpies of the inlet and outlet streams are:

Inlet: 334.9 kJ.kg-t ' Outlet 2726.5 kJ.kg-t

\
I
 64 CHAPTER 2. The Fit'st Inw atxd Otlxer Basic Con.cepts

Steam flows at steady state ttu'ough a converging, insulated nozzle,25 cm long and
u2.31.
with an inlet diametel of 5 cm. At the nozzle entrallce (state 1), the tempela.ture and
pressure are325"C and 700 kPa and the velocity is 30 m.s-1. At the nozzle exit (state 2),
the steam temper:ature and plessure arc240oC and 350 kPa. Ploperty values ale:
Ht --3112.-5 kT.kg-r Vr = 388.61 cm3.g-l
Hz:2945.7 kJ'kg-t Vz= 667.75 cm3.g-r
What is the velocity of the steam at the nozzle exit, and what is the exit diameter?

Irr the following take Cy l'oC-l fol nihogen

g.2.32. = 20.8 and Cp = 29.1 J'mol- gas:

(a) Thlee moles of nitrogen at 30oC, contained in a ligid vessel, is heated to 250oC. How
much heat is required ifthe vessel has a negligible heat capacity? If the vessel weighs
100 kg and has a heat capacity of 0.5 kJ.kg-t."C-1, how much heat is required?
Four-moles of nitlogen at 20Ogeis-eontained in-a-piston/eylinder-a.r+a.ngerxent- ---
-(b). How much heat must be extracted fi-om this system, which is kept at constant pres-
-
sure, to cool it to 40'C if the heat capacity of the piston and cylinder is neglected?

2.33. In the following take Cy - 5 and Cp = 7 (Btu)(lb mole)-t1"p;-t for nitrogen gas:

(a) Thee pound moles of nitrogen at 70("F), contained in a rigid vessel, is heated
to 350('F). How much heat is required if the vessel has a negligible heat capac-
ity? Ifir weighs 200(1br) and has a heat capaciry of 0.12(Btu)(lb,)-r('F)-r, how
much heat is required?
(&) Fourpound moles of nitrogen at 400('F) is contained in apiston/cylinder allangement.
How much heat must be exftacted fiom this system, which is kept at constant pres-
sure, to cool it to 150('F) if the heat capacity of the piston and cylinder is neglected?

2.34. Find an equation for the work of reversible, isothermal compression of mol of gas in
/. a piston/cylinder. assembly if the molar volume of the gas is given by
1

RT
. V=V+b
where & and R are positive constants.

2.35. Steam at 200(psia) and 600("F) [state l] enters a tur:bine through a 3-inch-diameter'
pipe with a velocity of l0(ft)'s-1. The exhaust from the turbine is carried through a
1O-inch-diametel pipe and is at 5(psia) and 200('F) [state 2]. What is the power output
of the turbine?

Hr:1322.6(BtuXlbm)-1 Vr = 3.058(ft)3(tu,o)
Hz= tt48.6(8tu)(lbil-r vz = 78.14(ft)3(1b,)-t
2.36. Steam at 1400 kPa and 350"C [state 1] enters a turbine thlough a pipe that is 8 cm in
diameter, at a mass flow rate of 0.1 kg.s-I. The exhaust from the turbine is carried
ttu'ough a 25-cm-diameter pipe and is at 50 kPa and 100"C fstate 2]. What is the power
output of the turbine?
 2.1 1 . Pfobletns 65

Hr = 3150.7 kJ.kg-t Vr =0.20024 m3.ks-l

Hz= 2682.6 kJ.kn-r Vz = 3.4181 m3.kg-l

Ht=21.11lcl.mol-l Vt:23.40l-.mo1-r
Hz:23.78 kJ.mol-l Vz = 0.i58i L.mol-l
-- - dioxide gas-eutersa-water-eooled-eornpr:essoFat eonditions-pq
i --238;earbon
\ = 50('F), anJ is discharged at conditions
=-15(psia)-and
p2 520(psia) and Zz 200(.F). The
= =
enteting CO2 flows through a 4-inch-diarneter pipe with a velocity of 20(ft).s-I, ald
1 is discharged thlough a l-inch-diameter pipe. The shaft work suiplie{ ro the com-
' pressot' is 5360(Btut0b mole)-I. What is ai" h"uuo'-rf.. rate from the compressoL
in
(Btu)'h- I
?

Hl = 307(Bhrxlbm)-r h = 9.25(ft)30bil-r
r1z = 330(Btu)(lb.)-r yz
= 0.2g(fD30br)-r

a.z 2.39. Show that W and Qfor an arbitrary mechanically reversible nonflow process are given by:

f-
w=Jvdn-^ev) r
e=^H-J vdp
t- ' z,4yone kiloglam of air is he pressure from an initial state of
300 K and I bal until its v a,u , and A.i.1 for the process.
e,
Assume for air that pV/T I and Cp 29 J.mol-l.K-l.
=

2.42. Aflow calbrimeter like that shown in Figure 2.6 is used with a flow rate of 20 g.min-l
of the fluid being tested and a constant temperature of 0"C ledving the constant-
temperature bath. The steady-state'temperature at section two (Tf ii measured as a
function of the power supplied to the heater (P), to obtain the data shown in the tabie
below. What is the average specific heat of the substance tested over the temperature
range fiom 0'C to 10'C? What is the average specific heat from 90.C to 100"C? What
is the average specific heat over the entire range tested? Describe how you would use
this data to derive an expression for the specific heat as a function of temDerature.
 66 CHAPTER 2. The First Law anri Otlrcr Basic Conceprs

T^ lo(- r0 20 30 40 50 60 70 80 90 r00
Ptw 55 1 1.0 16.6 22.3 280 33.7 39.6 45.4 5l .3 57.3

{/,,/ '-2.43- Like the flow calolimeter of Figure 2.6, aparticular sing.le-cup coffee maker uses
electric heating element to
an
heat a steady flow of water ftomZZ'C to gg.C. It heats
fluid ounces of water (with a mass of 237 g) in 60 s. Estimate the power.requirement
8
of the heater during this process. You may assume the specific heat of water- is con-
stant at 4.1 8 J'g-t '"9-t.
2.44. (a) An incompressible fluid (p = constant) flows thr.ough a pipe of col.lstant cross_
sectional arca. If the.flow is steady, show that velocity z and volumetr.ic flow rate
q ar€ constant.
(b) A chemically reactive gas stream flows steadily ttu.ough a pipe of constant
-pressur:e-vary-w.ith pi.pe--iength Wiieh-of
the following quantities are necessar.ily coustant: th , i, q, u?
--
2.45. The
-cross-sectional-ar:eaJempel:atu.l:eland
balance pr.ovides a.basis for estimating pressure drop owing
to fr For steady flow of an incompressiblJ iluid in a hor.izontal
pipe cdonal area, it may be written,
AP2
*+ ,fnCu2 =O
where/p is the Fanning friction factor. Churchilll3 gives the following expression for
/p for turbulent flow:
/ r \ oer )-2
fr=0.3305 {nlo.zl+
rr "+(Rti j,l
Here, Re is the Reynolds number and elD is the dimensionless pipe roughness. For
pipe flow, Re = upDlp, where D is pipe diameter and is dynarnic viscosity. The flow
' 4
is turbulent for Re > 3000.
Consider the flow of liquid water at 25'C. Fol one of the sets of conditions siven
below, determinefi (in kg.s-l) and Lp/LL (in kpa.rn-r). Assume e ,zD 0.000i For
=
liquid water at25oC, p = 996 kg.p-3, and 4 = 9.0 x l0-4 kg.m-I.5-1. Ver.ify that the
flow is tut'bulent.
(a) D=2cm,u=lm.s-l
(b) D=5cm,u= 1m.s-l
(c) D=2cm,u=5m.s-1
(d) D=5cm,u=5m.s-l

92.46. Ethylene enters a turbine ar 10 bar and 450 K, and exhausts at l(atm) and 325 K. For
= 4.5 kg's-I, determine the cost c of the tui-bine. state any assumptions you make.
rit

Data : Hr=76t.r Hz= 536.9 kJ.kg-r C/$ = (15,200)

ilvi,llrW;05t3
t3,q,lChE J., vol.
19, pp. 375-3't6,19.13.
2.1 L Problents
o/

2'47 ' The heating of a home to increase its tempelature must be modeled
as al.l opel system
because expansiotl of the household air at constant
illessure results in leakage ofair to
the outdool's. Assuming that the molar properties oi air leaving
the home ar.e the same
as those of the ail in the home, show that erergy and
mole bJances yreld the follorv-
ing differential equation:

Q =-Pv+*r!
ar 4t
Here,tQ is the late of heat h'ansfer to the air in the home, and / is trme.
euantities p,
V, n, and U refer: to the air.in the home.

2'48' (a) Water flows through the nozzle of a gardentrose. Find an expression
for nr i1
tel'ms of li'e pressure p,, ambient prcssufe p2, inside hose diameter.Dl, and

for constaltt temperatul e.

ffi:ffi,H#5P#:va;:+",,:;
(&) In fact, th_e frow cannot be truly isothermal: we expect
Tz > Tr, owing to fluid
fi'iction. Hence, H2- Ht = C(72- T) + (pz- p)/j,whereCis the
specific heat
of water'. Dircctionally, how would inclusion of the'temperature change
uif."t tt
value ofri as found in part (a)? "