Chapter 6

Thermochemistry

AboAhmed 3loom 0543122883

 Energy Changes in Chemical Reactions
‫تغيرات الطاقة في التفاعالت الكيميائية‬
Heat is the transfer of thermal energy between
two bodies that are at different temperatures.
‫عملية انتقال الطاقة الحرارية بين االجسام المحتلفة في درجة الحرارة‬
Temperature is a measure of the thermal energy.
‫درجة الحرارة تعتبر مقاس للطاقة الحرارية‬

Temperature = Thermal Energy

‫درجة الحرارة ال تساوي الطاقة الحرارية‬
Thermochemistry is the study of heat change in
chemical reactions.

‫ دراسة تغيرات الحرارة في التفاعالت الكيميائية‬: ‫الكيمياء الحرارية‬

2
AboAhmed 3loom 0543122883
The system is the specific part of the universe that is of interest
in the study.

The surroundings are the rest of the universe outside the

system.

open closed isolated

Exchange: mass & energy energy nothing 3

Exothermic process is any process that gives off heat –
transfers thermal energy from the system to the surroundings.

2H2 (g) + O2 (g) 2H2O (l) + energy

H2O (g) H2O (l) + energy

Endothermic process is any process in which heat has to be
supplied to the system from the surroundings.

energy + 2HgO (s) 2Hg (l) + O2 (g)

energy + H2O (s) H2O (l)

4
AboAhmed 3loom 0543122883
Schematic of Exothermic and Endothermic Processes

AboAhmed 3loom 0543122883 5

 Thermodynamics is the scientific study of the
interconversion of heat and other kinds of energy.

State functions are properties that are determined by the state

of the system, regardless of how that condition was achieved.
energy, pressure, volume, temperature

DE = Efinal - Einitial
DP = Pfinal - Pinitial

DV = Vfinal - Vinitial
DT = Tfinal - Tinitial

Potential energy of hiker 1 and hiker 2

is the same even though they took
6
different paths.
First law of thermodynamics – energy can be
converted from one form to another, but cannot be
created or destroyed.

DEsystem + DEsurroundings = 0
or
DEsystem = -DEsurroundings

C3H8 + 5O2 3CO2 + 4H2O

Exothermic chemical reaction!

Chemical energy lost by combustion = Energy gained by the surroundings

7
system surroundings
 Another form of the first law for DEsystem
DE = q + w
DE is the change in internal energy of a system
q is the heat exchange between the system and the surroundings
w is the work done on (or by) the system
w = -PDV when a gas expands against a constant external pressure

8
AboAhmed 3loom 0543122883
 Work Done On the System
w=Fxd
DV > 0
w = -P DV
-PDV < 0
F
P x V = 2 x d3 = F x d = w wsys < 0
d

Work is not a
state function.

Dw = wfinal - winitial initial final

The units for work done by or on a gas are liters atmospheres.
9
1 L . atm = 101.3 J
A sample of nitrogen gas expands in volume from 1.6 L to 5.4 L
at constant temperature. What is the work done in joules if the
gas expands (a) against a vacuum and (b) against a constant
pressure of 3.7 atm?

w = -P DV

(a) DV = 5.4 L – 1.6 L = 3.8 L P = 0 atm

W = -0 atm x 3.8 L = 0 L•atm = 0 joules

(b) DV = 5.4 L – 1.6 L = 3.8 L P = 3.7 atm

w = -3.7 atm x 3.8 L = -14.1 L•atm

w = -14.1 x 101.3 J = -1430 J

AboAhmed 3loom 0543122883 10
Enthalpy and the First Law of Thermodynamics

DE = q + w
At constant pressure:
q = DH and w = -PDV
DE = DH - PDV
DH = DE + P DV

11
AboAhmed 3loom 0543122883
 Enthalpy (H) is used to quantify the heat flow into or out of a
system in a process that occurs at constant pressure.
‫المحتوى الحراري هو كمية تستخدم للتعبير عن تدفق الحرارة من و الى النظام تحت‬
‫ضغط ثابت‬
DH = H (products) – H (reactants)
DH = heat given off or absorbed during a reaction at constant pressure
‫ هي الحرارة المنطلقة أو الممتصة من التفاعل تحت ضغط‬: ‫التغير في المحتوى الحراري‬
‫ثابت‬

‫المحتوى الحراري للنواتج أكبر من المتفاعالت المحتوى الحراري للنواتج أقل من المتفاعالت‬
Hproducts < Hreactants Hproducts > Hreactants
12
DH < 0 DH > 0
 Thermochemical Equations

‫المحتوى الحراري للنواتج أكبر من المتفاعالت‬

Is DH negative or positive?

System absorbs heat

Endothermic

DH > 0

6.01 kJ are absorbed for every 1 mole of ice that

melts at 00C and 1 atm.

H2O (s) H2O (l) DH = 6.01 kJ/mol

13
AboAhmed 3loom 0543122883
 Thermochemical Equations

‫المحتوى الحراري للنواتج أقل من المتفاعالت‬

Is DH negative or positive?

System gives off heat

Exothermic

DH < 0

890.4 kJ are released for every 1 mole of methane

that is combusted at 250C and 1 atm.

CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (l) DH = -890.4 kJ/mol
14
AboAhmed 3loom 0543122883
 Thermochemical Equations
• The stoichiometric coefficients always refer to the number
of moles of a substance
‫المعامالت في المعادالت الكيميائية تشير الى عدد الموالت للمادة‬
H2O (s) H2O (l) DH = 6.01 kJ/mol

• If you reverse a reaction, the sign of DH changes

‫ اشارة التغير في المحتوى الحراري يتم عكسها‬, ‫عند عكس التفاعل‬
H2O (l) H2O (s) DH = -6.01 kJ/mol
• If you multiply both sides of the equation by a factor n,
then DH must change by the same factor n.
‫ يضرب أيضا التغير في المحتوى الحراري‬, ‫عند ضرب المعامالت في التفاعل بعدد معين‬

2H2O (s) 2H2O (l) DH = 2 x 6.01 = 12.0 kJ

AboAhmed 3loom 0543122883 15

 Thermochemical Equations

• The physical states of all reactants and products must be

specified in thermochemical equations.
‫حاالت المواد يجب كتابتها في المعادالت الكيميائية‬
H2O (s) H2O (l) DH = 6.01 kJ/mol
H2O (l) H2O (g) DH = 44.0 kJ/mol
How much heat is evolved when 266 g of white phosphorus (P4)
burn in air? P4 (s) + 5O2 (g) P4O10 (s) DH = -3013 kJ/mol
123.9 g/ mol = P4

266 P4
= 2.14 mol P4
123.9 P4
3013 kJ
= 2.14 mol P4 x = 6470 kJ
1 mol P4
16
AboAhmed 3loom 0543122883
 A Comparison of DH and DE

2Na (s) + 2H2O (l) 2NaOH (aq) + H2 (g) DH = -367.5 kJ/mol

DE = DH - PDV At 25 oC, 1 mole H2 = 24.5 L at 1 atm

PDV = 1 atm x 24.5 L = 2.5 kJ

DE = -367.5 kJ/mol – 2.5 kJ/mol = -370.0 kJ/mol
The reason DH is smaller than DE in magnitude is that some of the internal
energy released is used to do gas expansion work, so less heat is evolved.
‫ هو أن جزء من الطاقة يتحول الى شغل‬DE ‫ أقل من‬DH ‫السبب في أن‬

17
AboAhmed 3loom 0543122883
 A Comparison of DH and DE

To calculate the internal energy change of a gaseous reaction

is to assume ideal gas behavior and constant temperature

AboAhmed 3loom 0543122883

AboAhmed 3loom 0543122883 19
The specific heat (s) of a substance is the amount of heat (q)
required to raise the temperature of one gram of the
substance by one degree Celsius.

The heat capacity (C) of a substance is the amount of heat

(q) required to raise the temperature of a given quantity (m)
of the substance by one degree Celsius.
C=mxs

Heat (q) absorbed or released:

q = m x s x Dt
q = C x Dt
Dt = tfinal - tinitial

20
AboAhmed 3loom 0543122883
How much heat is given off when an 869 g iron bar cools
from 94oC to 5oC? s of Fe = 0.444 J/g • oC

Dt = tfinal – tinitial = 5oC – 94oC = -89oC

q = msDt = 869 x 0.444 x –89oC = -34,000 J

21
AboAhmed 3loom 0543122883
AboAhmed 3loom 0543122883 22
 Standard Enthalpy of Formation and Reaction

Standard enthalpy of formation (DH0) is the heat change

f
that results when one mole of a compound is formed from
its elements at a pressure of 1 atm.

The standard enthalpy of formation of any element in its

most stable form is zero.

DH0f (O2) = 0 DH0f (C, graphite) = 0

DH0 (O3) = 142 kJ/mol DH0f (C, diamond) = 1.90 kJ/mol

f 23
AboAhmed 3loom 0543122883
24
Benzene (C6H6) burns in air to produce carbon dioxide and
liquid water. How much heat is released per mole of benzene
combusted? The standard enthalpy of formation of benzene is
49.04 kJ/mol.

2C6H6 (l) + 15O2 (g) 12CO2 (g) + 6H2O (l)

DH0rxn = S nDH0f (products) - S mDHf0 (reactants)

DH0rxn = [ 12DH0f (CO2) + 6DH0f (H2O)] - [ 2DH0f (C6H6)]

DH0rxn = [ 12x–393.5 + 6x–187.6 ] – [ 2x49.04 ] = -5946 kJ

-5946 kJ
= - 2973 kJ/mol C6H6
2 mol

AboAhmed 3loom 0543122883 25

 0 ) is the enthalpy of
The standard enthalpy of reaction (DHrxn
a reaction carried out at 1 atm.

aA + bB cC + dD

DH0rxn = [ cDH0f (C) + dDH0f (D) ] - [ aDH0f (A) + bDH0f (B) ]

DH0rxn = S nDH0f (products) - S mDHf0 (reactants)

AboAhmed 3loom 0543122883 26

Hess’s Law: When reactants are converted to products, the
change in enthalpy is the same whether the reaction takes
place in one step or in a series of steps.

(Enthalpy is a state function. It doesn’t matter how you get

there, only where you start and end.)

AboAhmed 3loom 0543122883 27

Let’s say we are interested in the standard enthalpy of formation of
carbon monoxide (CO).

However, burning graphite also produces some carbon dioxide (CO2), so

we cannot measure the enthalpy change for CO directly.
We must employ an indirect route, based on Hess’s law.
It is possible to carry out the following two separate reactions:

First, we reverse Equation (b) to get

we carry out the operation (a) + (c) and obtain

AboAhmed 3loom 0543122883

C (graphite) + 1/2O2 (g) CO (g)
CO (g) + 1/2O2 (g) CO2 (g)
C (graphite) + O2 (g) CO2 (g)

29
Calculate the standard enthalpy of formation of CS2 (l) given
that:
C(graphite) + O2 (g) CO2 (g) DH0rxn = -393.5 kJ/mol
S(rhombic) + O2 (g) SO2 (g) DH0rxn = -296.1 kJ/mol
CS2(l) + 3O2 (g) CO2 (g) + 2SO2 (g) DHrxn
0 = -1072 kJ/mol

1. Write the enthalpy of formation reaction for CS2

C(graphite) + 2S(rhombic) CS2 (l)

2. Add the given rxns so that the result is the desired rxn.
C(graphite) + O2 (g) CO2 (g) DH0rxn = -393.5 kJ/mol
2S(rhombic) + 2O2 (g) 2SO2 (g) DH0rxn = -296.1 kJ/mol x 2
+ CO2(g) + 2SO2 (g) CS2 (l) + 3O2 (g) DHrxn
0 = +1072 kJ/mol

C(graphite) + 2S(rhombic) CS2 (l)

DH0rxn= -393.5 + (2x-296.1) + 1072 = 86.3 kJ/mol
30