Updated: 1 February 2019 Print version

Lecture #6
Kinetic and Thermodynamics: Some
T
hermo Fundamentals
(
Stumm & Morgan, Chapt.2-3 )

David Reckhow CEE 680 #6 (Benja 1

Chapt 2: Basics
Thermodynamics
 Will tell you
 which reactions are favorable or “Possible”
 composition of systems at equilibrium Sets limits
 Won’t tell you
 how quickly the reactions proceed
 good for systems with constant P & T
 Air:
1.0 atm at sea level
 Water: 1.0 atm for each additional 10.7 m of
water
 Earth: wt of overlying rock and soil
 Governing property @ const. T&P is the Gibbs Free
Energy
 for constant T&V, it is the Helmholtz Free Energy

David Reckhow CEE 680 #6 2

Thermodynamics: Examples
Removal of P from wastewater by
is it possible?
Alum
What is best pH? Ye
What is the final P s
concentration?
How much is removed in treatment No
system?
Ammonia stripping
best pH?
Acid rain
pH of “pure” rainwater?

David Reckhow CEE 680 #6 3

Open & Closed Systems
Closed Systems
 No significant flux of material into or out of
system
 Like an isolated beaker of water
 Steady state condition is the true
chemical equilibrium
Open systems
 Mass movement across system
boundary from or to outside
world
 More realistic, but more
complicated
 Steady state condition may not be true chemical
David Reckhowequilibrium,
CEEdue
680 #6 to continuous perturbation 4
 Universe
Laws of Thermodynamics
System
1st Law
Conservation of energy
 best you can hope for is to “break even”
 dE=dq-dw E = internal energy
2nd Law q = heat transfer to the system
w = work done by the system
Entropy of the universe tends to
increase

 dS
you > dq /T,
sys can’t evenfor irreversible
“break even”
 processes
dSuniv = dSsys + dS surr  0 And since: dSsurr =
3rd -dq/T
Entropy is zero for a perfect crystal at absolute
Law
zero
David Reckhow CEE 680 #6 5
Combining 1st & 2nd Laws
Internal Energy Change for reversible
 dE = dq – dw
processes And since: dSsys = dq /T
 dE = TdSsys – dw
 dE = TdSsys – pdV When only pV work is done on
the surroundings
But for a system not at equilibrium that is undergoing
an irreversibleprocess, entropy must increase beyond
dq/T
 dE < – pdV <0 dSsys = di S +
– TdSsys
sys +
dq /T
And taking into account the entropy increase, diS, we
can maintain the equality
 dE = TdSsys – TdiS – pdV

David Reckhow CEE 680 #6 6

Enthalpy
A fundamental thermodynamic variable
enthalpy change is equal to heat of reaction
(for systems at constant pressure)
H<0, heat is given dH = TdS + V dp
off dH = dq + V dp
 exothermic dH = dq, for constant
H>0, heat is pressure processes with
absorbed
H can be calculated
external work (w=0)
no
standard
from enthalpies of formation
 endothermic

(Hof )
 available in many texts
 e.g., Snoeyink & Jenkins, Table 3-
1 i of
David Reckhow CEE 680 #6

H o   H
7
Example
Evaporation of H2O(g
water )
 H2O(l) = H2O(g) H2O(g H2O(l)
 o
  i  of
H2O (l)
H H )

 1mole  57.80

mole  1mole  68.32
kcal
mole


 10.52
kcal kcal
H>0, heat is absorbed
 endothermic

 However, this does not tell us if the reaction

is favorable, or proceeds spontaneously
 to answer this we need to know the entropy change

David Reckhow CEE 680 #6 8

 Thermodynamic Constants for Species of Importance in Water
Chemistry (Table 3-1 from Snoeyink & Jenkins) Part I

 o  o  o  o
Species H f Gf Species H f Gf
kcal/mole kcal/mole kcal/mole kcal/mole
+2
Ca (aq) -129.77 -132.18 CO3-2 (aq) -161.63 -126.22
CaC03(s), calcite -288.45 -269.78 CH3COO-, -116.84 -89.0
acetate
CaO (s) -151.9 -144.4 H+ (aq) 0 0
C(s), graphite 0 0 H2 (g) 0 0
CO2(g) -94.05 -94.26 Fe+2 (aq) -21.0 -20.30
CO2(aq) -98.69 -92.31 Fe+3 (aq) -11.4 -2.52
CH4 (g) -17.889 -12.140 Fe(OH)3 (s) -197.0 -166.0
H2CO3 (aq) -167.0 -149.00 Mn+2 (aq) -53.3 -54.4
HCO3- (aq) -165.18 -140.31 MnO2 (s) -124.2 -111.1

Conversion: 1kcal = 4.184 kJ

David Reckhow CEE 680 #6 9
Thermodynamic Constants for Species of Importance in Water
Chemistry (Table 3-1 from Snoeyink & Jenkins) Part II
 o  o  o  o
Species H f Gf Species H f Gf
kcal/mole kcal/mole kcal/mole kcal/mole
Mg (aq)
+2
-110.41 -108.99 O2 (g) 0 0
Mg(OH)2 (s) -221.00 -199.27 OH- (aq) -54.957 -37.595
NO3- (aq) -49.372 -26.43 H2O (g) -57.7979 -54.6357
NH3 (g) -11.04 -3.976 H2O (l) -68.3174 -56.690
-2
NH3 (aq) -19.32 -6.37 SO -216.90 -177.34
4
NH4+ (aq) -31.74 -19.00 HS (aq) -4.22 3.01
HNO3 (aq) -49.372 -26.41 H2S(g) -4.815 -7.892
O2 (aq) -3.9 3.93 H2S(aq) -9.4 -6.54

Conversion: 1kcal = 4.184 kJ

David Reckhow CEE 680 #6 10

 A measure of a
Entropy system’s randomness
remove the
V1, c1 V2, c2 partition and
T=0
randomness
increases
2nd law of Thermo.
T=1 
i f
S  
 o
Spontaneous in So
T=2 isolated system
 Like water running
downhill
 Or hot objects
T=large heating colder ones
David Reckhow CEE 680 #6 11
Gibbs Free Energy
Combines enthalpy and entropy
1st and 2nd laws of thermodynamics
Determines whether a reaction is favorable
or spontaneous
Practical form is based on an arbitrary
datum
the pure and most stable form of each element
at standard state
 o  o  o
G  H T S
David Reckhow CEE 680 #6 12
Standard State
About:
Standard State 1 mole/L for dissolved substances
Conditions: 1 atmosphere for gases
Unit activity

Rarely
(a=1) encountered in practice; but easier to
base calculations on
State variables: Go, µo
Non-standard State
Conditions:
 Non-unit activity, often quite low
This is the “real world”
State Variables: G, µ

David Reckhow CEE 680 #6 13

Solving problems Recall,
withatG any T &   i
o
 i
Go

 G can be calculated at 25 P:
 C o

from standard gibbs free But for STP, we

  i G
energies
formationof(Go f) use: o
 f
Go
 
These are essentially G’s for the
formation of chemical substances
from the most stable forms of their
constituent elements
 available in many texts
 e.g., Stumm & Morgan, Appendix 3
 e.g., Benjamin, Table 2.1
In: kJ/mole
 e.g., Snoeyink & Jenkins, Table 3-1
In: kcal/mole
Conversion: 1kcal =
4.184 kJ
David Reckhow CEE 680 #6 14
Ammonia Problem (1/7)
Determine Go for dissolution of ammonia in
water at 25oC
NH 3 (g)  NH 3 (aq)
Basedon example 2.5 in text
Two approaches
 A. Determine Go directly from individual Gof ’s
 The easiest way

 B. Determine Go from Ho and So


G o   H o T S
o

David Reckhow CEE 680 #6 15

 Ammonia Problem (2/7)
A. Determine Go directly from individual Gof
’sGet thermodynamic data
 from Appendix A (Benjamin) or Appendix 3
(S&M)
Expand equation and  
substitute
NH (
data
g ) of  NH ( g ) NH (aq) of  NH 3 (aq
 o  o
G
3
G
3 3
G
G     )
 (1)(16.48)  (1)
(26.57)
 10.09 Units are kJ/mole
G

Formation from Entropy
the Elements
Species Gfo (kJ Hfo (kJ So (J mol- Reference
1
mol-1) mol-1) K-1)
NH3(g) -16.48 -46.1 192 NBS
NH3(aq) -26.57 -80.29 111 NBS
NH4+(aq) -79.37 -132.5 113.4 NBS

David Reckhow CEE 680 #6 16

Ammonia Problem (3/7)
B. Determine Go from Ho and So
Get thermodynamic data from Appendix A (or
3)
Expand equations and substitute data

 o
 NH 3 ( g )  of  NH 3 ( g )
  NH (aq)  f  NH 3
H H H o(aq)
3

 (1)(46.1)  (1)

i of

H  
o H (80.29)
 34.19 Units are kJ/mole
   NH
  i
 o 
S
NH 3 ( g )
S
NH
o 3( g ) 3 (aq)
So
NH 3 (aq)

o

 (1)(192)  (1)
(111)
 81 Units are J/mole/oK
S o S
David Reckhow CEE 680 #6 17
Ammonia Problem (4/7)
Now combine and solve for
 Go

G o   H o T S o 1kJ
1000 
 10.04  (273.16
 (34.19) Units arekJ/mole
25) J

(81)
 Conclusion: reaction is spontaneous since G <0  o

 Lingering question: what actually happens when we’re

not at standard state conditions (i.e., when activity isn’t
equal to one)?

David Reckhow CEE 680 #6 18

Chemical Potential
Like a Gibbs Free Energy normalized per
mole
a function of activity and
temperature kJ
i  G 
  i T ,P
kJ/mole  n


i   io  RT ln
ai
This term corrects for the fact
Standard state (unit activity) that we’re not at unit activity

David Reckhow CEE 680 #6 19

Example
Activities in concentrated NaCl
solution
S&M: Example 2.3 (pg 40)

David Reckhow CEE 680 #6 20

General Condition
And relating to the change in G for
complete conversion to products
G   i   i
 o
i and  i
 Go
o  RT ln ai 
 
i i
o 

i i
   RT  i ln aCc a dD
ai

G 
G o
 RT ln Q where Q
A B
a a ab

For the reaction: aA  bB  cC 

dD
David Reckhow CEE 680 #6 21
Ammonia problem (5/7)
Now lets see what the G is for the following
non- standard conditions
 [NH3(aq)] = 10-3 M
pNH3 = 10-4 atm
Now we need to determine Q
Recall the NH 3 (g)  NH 3 (aq)
reaction:
So 1 3
a NH 3
: Q (aq ) 10
 10  4 
NH 3
a1( g ) 10

David Reckhow CEE 680 #6 22

 R=1.987 x10-3 kcal/mole oK
Ammonia problem (6/7) =8.314 x10-3 kJ/mole oK
Now substitute back into the equation for G


G  G o  RT ln Q
 10.04  (0.008314)(273.16  25)
ln(10)
 Units are
4.33 kJ/mole
Conclusion: the reaction is still spontaneous at
these non-standard concentrations
 i.e., the reaction will proceed toward the right
Another lingering question: how far to the right will
it proceed before it reaches equilibrium and stops?
 To answer this we need to determine “K”

David Reckhow CEE 680 #6 23

Equilibrium Quotients
at Equilibrium G=0, 0  G o  RT ln K
so:
Where K is defined as the

 RT
and:
o
ln K quotient (Q) at equilibrium
G
 2.303RT log and is generally referred to
K as the “equilibrium
or: constant”
K  a a , at equilibrium
C
c dD

A B
log K  G  o a a ab
 2.303RT

David Reckhow CEE 680 #6 24

Ammonia problem (7/7) R=1.987 x10-3 kcal/mole oK
=8.314 x10-3 kJ/mole oK
To determine the equilibrium position of
ammonia dissolution, we need the
equilibrium constant, K
log K   o
G
 2.303RT
K  101.76
10.04

 57.4
2.303(0.008314)(273.16 
25)
So as we approach equilibrium, Q will approach
 1.76
the value of K, which is 57.4
1 3
a NH 3
Q 10 
(aq )

NH 3
a1( g ) 10 4 10
David Reckhow CEE 680 #6 25
Quotients (cont.)
more generally, for non-equilibrium conditions,
we can combine:

G  G o  RT ln Q
 RT ln K  RT ln 
G  2.303RT
Q  
 Q  log Q K

 RT ln
K
and if,
G<0, (Q/K)<1, and equilibrium lies to the
right
G>0, (Q/K)>1, and equilibrium lies to the left
David Reckhow
G=0, (Q/K)=1,
CEE 680 #6
and system is at equilibrium 26
Gibbs Energy of a System
Fig. 2.5
G Changes as reaction Pg. 45
27
progresses due to
changing concentrations
G reaches a minimum at
the point of equilibrium

 dG
G
d
Extent of reaction
David Reckhow CEE 680 #6
 o
The Gf Conventio
Since the Go  G’s for the
values are essentially
n f
formation of chemical substances from the
“most stable” (reference) forms of their
constituent elements
The Gfo values for those most stable elemental
forms are zero, by definition
Examples
Zero-valent, Metallic Ag, Al, Fe, Mn, Pb, Zn
graphite-C, white-P, rhombic-S
diatomic H2, I2, N2, O2

David Reckhow CEE 680 #6 28

 Simple examples
Reaction 
Go
H2 (g) + S(s) = H2S(aq)
-27.87
H2 (g) + S(s) = H2S(g) -33.56
-300.2
O2 (g) + S(s) = SO2 (g)
-43.3
Hg(l) + S(s) = HgS(s) -237.18
H2 (g) + ½O2 (g) = H2O(l) 16.32
 In all of these cases reactants have a Gfo equal to zero, i.e., they
O2(g) =are
O2the
(aq)
reference forms of the elements
 so the Go is simply equal to the Gfo of the product
compound

David Reckhow CEE 680 #6 29

 30

S&M: Example Fig. 2.7

(pg 46)
Pg. 48
2.4
Dissolution ofCO2
CO2 (g) = CO2 (aq)


G  H T S

David Reckhow CEE 680 #6

 Hexavalent Cr
is now a big
regulatory issue
Chromium Example
(1/6)

David Reckhow
Example 2.10 from (pg 111): Benjamin, 2002
CEE 680 #6 31
Chromium Example (2/6)

 o
G
log K 
 2.303RT

Example 2.10 from (pg 111): Benjamin, 2002

David Reckhow CEE 680 #6 32
Chromium Example (3/6)

Example 2.10 from (pg 111): Benjamin, 2002

David Reckhow CEE 680 #6 33
Chromium Example (4/6)

Example 2.10 from (pg 111): Benjamin, 2002

David Reckhow CEE 680 #6 34
Chromium Example (5/6)

Example 2.10 from (pg 111): Benjamin, 2002

David Reckhow CEE 680 #6 35
 Chromium
Example
#6 (6/6) 36

Minimum
Gibbs free
energy is
where ΔGr = 0

Example 2.10 from

(pg 111): Benjamin,
2002
David Reckhow CEE 680
 Alternative Direct Calculation −2
2𝐶𝑂
𝑂
7𝐶
𝐶𝐶
Assume standard activity for 𝐾𝐾=
𝐻
𝐻𝐶𝐶
𝑂
𝑂− 2
4

water
Combine equilibrium and mass balance
equations − −2
𝑡0.1
𝑡𝑡𝑡 𝑡 𝑡=
𝑡 𝑡𝐶 𝐶𝐶 𝑂
4𝐶
𝑂𝐶
𝐻𝐻
𝐶 +2
𝑂
𝐶
27𝑂𝐶𝐶
Set bichromate = 72
𝑂
𝐶
2 𝑂𝐶𝐶 −2 =0.1-x
x −2
0.05 − 0.5𝑥
𝑂𝐶
27𝑂𝐶𝐶
𝐾𝐾= 32.5 = − 2 = 2𝑥 𝑥
𝐻𝑂
𝐻
4𝐶
𝐶
𝑂
32.5𝑥𝑥2 + 0.5𝑥
𝑥− 0.05 = 0
And using the quadratic formula

−𝑏
𝑏± 𝑏2 −𝑎4𝑎
𝑎 −0.5 ± 0.25 −
𝑥=
𝑥 = 6.5 = 0.032278
2𝑎
𝑎 65
David Reckhow CEE 680 #6 37
Ionic Species & Redox
Convention
sGfo = 0, for
H2o +

this
Gf = 0, for
makes the hydrogen oxidation half reaction
aHreference point for Redox
 for: ½H2 (g) = H+ + e-, G = 0
oxidations and reductions
 must be coupled
 we only concern ourselves with the differences in G for

the two half reactions

David Reckhow CEE 680 #6 38

Temperature Effects on K
Need H (enthalpy change)
H < 0, exothermic (heat evolved)
H > 0, endothermic (heat
absorbed)
The Van’t Hoff Equation:
K2 
H o T2 T1
log K1
 2.303RT2T
Log K
1
recall
that:
  i 

H o
H of 1/T

David Reckhow CEE 680 #6 39

 Van’t Hoff 
G o   H o T S o
Equation  RT ln K   H o T S
o
Where does it come
ln K  
Ho
RT  
S

d ln R
K  Ho
RT 2
dT
K2 T2
H o T2 T1
K d ln K 

K2
log K
 2.303RT T

Ho
R
dT
T
2

1  T

ln KK 
1
2

Ho
R T1 T

1 2
1 1
David Reckhow CEE 680 #6 40
 80 #6 41

Home
Water
Heater
Gas
fired

From: Quick Guide Plumbing,

Creative Homeowner Press
David Reckhow CEE 6
 Thickness Loss of
of Scale in of Heat
Inches Transfer

Scale 1/16
Efficienc
y
15%
1/8 20%
1/4 39%
1/2 70%
3/4 90%
A cross section of 1 & 1/2" copper pipe Data: US National Bureau of
with a scale build-up of over 1/2" in Standards

thickness
Calcium scale formation on the inside of pipes and water heaters, on sinks, tubs, shower
doors and other water contact surfaces is a multi-million dollar problem for individuals and
businesses. A thin, one eighth inch layer of scale is such an effective insulator that it reduces
the efficiency of your water heater by 20%. This translates directly to increased energy cost
to attain the desired water temperature. Scale also increases the cost of equipment
maintenance and shortens equipment life. When these costs are added together, the price of
calcium scale is staggering

David Reckhow CEE 680 #6 42

Example Problem
Water is at equilibrium with calcium carbonate
at 25oC. It enters a house at 15oC, then is heated
to 60oC in a water heater.
Is the water supersaturated as it
 A. enters the house?
 B. leaves the water heater?

Solution to A.
1. Calculate Go
2. Determine K1 at 25oC
3. Determine Ho
4. Determine K2 at 15oC

David Reckhow CEE 680 #6 43

Solution
At neutral pH: CaCO3 (s) + H+ = HCO3- + Ca+2
 1. Calculate Go
 =-140.31-132.18-(-269.78) = -2.71 kcal
 2. Determine K1 at 25oC
Go=-RTlnK = -2.303RT*logK
 -2.71=-2.303(0.001987)298*logK =-1.364logK
 log K =1.99; K=101.99
 3. Determine Ho
 =-165.18-129.77-(-288.345) = -6.5 kcal
 4. Determine K2 at 15oC
 log (K2/101.99) = -6.5(288-298)/2.303(0.001987)288(298)=0.1655
 log K2 = 2.156

K2 = 102.16
David Reckhow CEE 680 #6 44
 Thermodynamic Constants for Species of Importance in
Water Chemistry (Table 3-1 from Snoeyink & Jenkins) Part I

 o  o  o  o
Species H f Gf Species H f Gf
kcal/mole kcal/mole kcal/mole kcal/mole
+2
Ca (aq) -129.77 -132.18 CO3-2 (aq) -161.63 -126.22
CaC03(s), calcite -288.45 -269.78 CH3COO-, -116.84 -89.0
acetate
CaO (s) -151.9 -144.4 H+ (aq) 0 0
C(s), graphite 0 0 H2 (g) 0 0
CO2(g) -94.05 -94.26 Fe+2 (aq) -21.0 -20.30
CO2(aq) -98.69 -92.31 Fe+3 (aq) -11.4 -2.52
CH4 (g) -17.889 -12.140 Fe(OH)3 (s) -197.0 -166.0
H2CO3 (aq) -167.0 -149.00 Mn+2 (aq) -53.3 -54.4
HCO3- (aq) -165.18 -140.31 MnO2 (s) -124.2 -111.1

David Reckhow CEE 680 #6 45

Thermodynamic Constants for Species of Importance in
Water Chemistry (Table 3-1 from Snoeyink & Jenkins) Part II
 o  o  o  o
Species H f Gf Species H f Gf
kcal/mole kcal/mole kcal/mole kcal/mole
Mg (aq)
+2
-110.41 -108.99 O2 (g) 0 0
Mg(OH)2 (s) -221.00 -199.27 OH- (aq) -54.957 -37.595
NO3- (aq) -49.372 -26.43 H2O (g) -57.7979 -54.6357
NH3 (g) -11.04 -3.976 H2O (l) -68.3174 -56.690
-2
NH3 (aq) -19.32 -6.37 SO -216.90 -177.34
4
NH4+ (aq) -31.74 -19.00 HS (aq) -4.22 3.01
HNO3 (aq) -49.372 -26.41 H2S(g) -4.815 -7.892
O2 (aq) -3.9 3.93 H2S(aq) -9.4 -6.54

David Reckhow CEE 680 #6 46

Solution (cont.)
Repeat step #4 for 60oC.
 4. Determine K2 at 60oC
 log (K3/101.99) = -6.5(333-298)/2.303(0.001987)333(298)=


-0.5
K3 = 101.49
 log K3 = 1.49
Compare K1 and K2 and K3
 what does this tell you about possible precipitation?
 As temp increases, solubility decreases

 This is an exothermic reaction, so rising temp

drives reaction to the left

David Reckhow CEE 680 #6 47

Le Chatelier’s Principle
A system at equilibrium, when subject to a
perturbation, responds in a way that tends
to minimize its effect
 If H>0 (endothermic), dlnK/dT >0, and K as T 
 if you heat endothermic reaction they will go further to the
right
 If H<0 (exothermic), dlnK/dT <0, and K as T 
 if you heat exdothermic reaction they will go back to the
left
d ln
K  
RT H o2
dT

David Reckhow CEE 680 #6 48

Pressure & Temp. effects
Temp
 Fig. 2.8
 Pg. 56

 T 
G   S
 o

Pressur   P
 o

e
  o

 P   V o
G T

David Reckhow CEE 680 #6 49

 To next lectur
e

DAR

David Reckhow CEE 680 #6 50