Chapter 6

Thermochemistry

Dr Mamoon Alokour
Energy is the capacity to do work.

• Radiant energy comes from the sun and is

earth’s primary energy source
• Thermal energy is the energy associated with the
random motion of atoms and molecules
• Chemical energy is the energy stored within the
bonds of chemical substances
• Nuclear energy is the energy stored within the
collection of neutrons and protons in the atom
• Potential energy is the energy available by virtue
of an object’s position 2
 Energy Changes in Chemical Reactions

Heat is the transfer of thermal energy between

two bodies that are at different temperatures.

Temperature is a measure of the thermal

energy.

Temperature = heat (thermal energy)

3
Thermochemistry is the study of heat change in chemical
reactions.
The system is the specific part of the universe that is of
interest in the study.

open closed isolated

Exchange: mass & energy energy nothing 4
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)

5
Schematic of Exothermic and Endothermic Processes

6
Exercise question:
Classify the followings as “exothermic” or “endothermic” process:

a) Combustion of petroleum
b) Evaporation of water
c) Nuclear fission
d) Cooking an egg
e) Mixing water and strong acids
f) Melting ice cubes
g) Burning candle
h) Condensation of water
i) Freezing of lakes
j) Boiling water
Ans: exothermic: a, c, e, g, h, i

7
 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

DU = Ufinal - Uinitial
DP = Pfinal - Pinitial

DV = Vfinal - Vinitial
DT = Tfinal - Tinitial

Example: Potential energy of hiker 1 and hiker 2 is the same

even though they took different paths. So, change in potential
energy is a state function 8
First law of thermodynamics – energy can be
converted from one form to another, but cannot be
created or destroyed.
DUsystem + DUsurroundings = 0
or
DUsystem = -DUsurroundings
Energy lost by the system = energy gained by the surroundings
or vica versa

S(s) + O2(g) → SO2(g)

Exothermic chemical reaction!
Chemical energy lost by combustion (of system) =
Energy gained by the surroundings

System is the reactants and products,

Suroundings are air, reaction container etc in this example
9
 Another form of the first law for ΔUsystem
ΔU = q + w
∆U 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 = – PΔ V when a gas expands against a constant external pressure

Table 6.1 Sign Conventions for Work and Heat

Process Sign
Work done by the system on the surroundings −
Work done on the system by the surroundings +
Heat absorbed by the system from the surroundings (endothermic process) +
Heat absorbed by the surroundings from the system (exothermic process) −

© McGraw-Hill Education. 6-10

Example(6.1): Calculate ΔE for a system undergoing an endothermic
process in which 15.6 kJ of heat flows and where 1.4 kJ of work is done
on the system.
Ans: 17.0 kJ

Example(6.2): A certain gas expands in volume from 2.0 L to 6.0 L at

constant temperature. Calculate the work done by the gas if it expands

(a) against a vacuum

(b) against a constant pressure of 1.2 atm

Ans: a) 0, b) -4.9  102 J

Example 6.3: A balloon is being inflated to its full extent by heating the air
inside it. In the final stages of this process, the volume of the balloon
changes from 4.00 ×106 L to 4.50 × 106 L by the addition of 1.3 × 108 J of
energy as heat. Assuming that the balloon expands against a constant
pressure of 1.0 atm, calculate ΔE for the process. (To convert between L
atm and J, use 1 L atm = 101.3 J.)
Ans: 8 ×107J
Enthalpy and the First Law of
Thermodynamics
ΔU =q +w
At constant pressure:

q = ΔH and w = – P ΔV
ΔU = ΔH – P ΔV
Δ H = Δ U + P ΔV

© McGraw-Hill Education. 6-13

 Enthalpy
Enthalpy (H) is used to quantify the heat flow into or out of a system in
a process that occurs at constant pressure.
ΔH  H  products  – H reactants 
ΔH = heat given off or absorbed during a reaction at constant pressure

Hproducts > Hreactants Hproducts < Hreactants

ΔH > 0 ΔH < 0

© McGraw-Hill Education. 6-14

 Thermochemical Equations (1 of 4)

Is ΔH negative or positive?
System absorbs heat
Endothermic

ΔH > 0

6.01kJ are absorbed for every 1 mole of ice that melts at

0 C and 1 atm.
H2O  s   H2O  l  ΔH = 6.01 kJ mol

© McGraw-Hill Education. 6-15

 Thermochemical Equations (2 of 4)

Is ΔH negative or positive?

System gives off heat

Exothermic

ΔH < 0

890.4kJ are released for every 1 mole of methane that is

combusted at 25 C and1 atm.
CH4  g  + 2O2  g   CO2  g   2H2O  l  ΔH = – 890.4kJ mol

© McGraw-Hill Education. 6-16

 Thermochemical Equations (3 of 4)

The stoichiometric coefficients always refer to the number

of moles of a substance
H2O  s   H2O  l  ΔH = 6.01 kJ mol

If you reverse a reaction, the sign of ∆H changes

H2O  l   H2O  s  ΔH = – 6.01 kJ mol

If you multiply both sides of the equation by a factor n,

then ΔH must change by the same factor n.
2H2O  s   2H2O  l  ΔH = 2 × 6.01 = 12.0kJ

© McGraw-Hill Education. 6-17

 Thermochemical Equations (4 of 4)

The physical states of all reactants and products must be

specified in thermochemical equations.

H2O  s   H2O  l  ΔH = 6.01 kJ mol

H2O  l   H2O  g  ΔH = 44.0 kJ mol

© McGraw-Hill Education. 6-18

Example (6.4): Given the thermochemical equation

2SO2(g) + O2(g) → 2SO3(g) ΔH = −198.2 kJ/mol

calculate the heat evolved when 87.9 g of SO2 (molar mass = 64.07 g/mol) is
converted to SO3.
Ans: 136 KJ

Example (6.5): When 1 mole of methane (CH4) is burned at constant pressure,

890 kJ of energy is released as heat. Calculate ΔH for a process in which a 5.8
g sample of methane is burned at constant pressure.
Ans: ΔH = heat flow =-320 kJ
Example(6.6): The combustion of pentane produces heat according
to the equation
C5H12(l) + 8O2(g) ⟶ 5CO2(g) + 6 H2O(l) ∆H°rxn= –3,510 kJ
How many grams of CO2 are produced per 2.50x103 kJ of heat
released?
(MCO2 = 44 g/mol) Ans: 157 g
Work done by a reaction involving gases at constant
pressure and temperature:
w = -P∆V
∆V = ∑Vproducts - ∑Vreactants
Since, for a reactant or product, V = nRT/P
Then:
∆V = ∑nproductsRT/P - ∑nreactantRT/P
= (∑nproducts - ∑nreactant)RT/P
or
= ∆nRT/P where ∆n=∑nproducts - ∑nreactant
Hence:
w = - P ∆V = - P∆nRT/P = - ∆nRT 21
∆n=∑nproducts - ∑nreactant
Note: do not consider the mole numbers of solids or liquids in the
reaction in calculation of ∆n since their molar volumes are
negligible compared to the molar volume of gases.
Example:
What is ∆n for the following reactions:
3A(g) + 2B(g) ⟶ 2C(g) + 3D(g) ∆n = (nC + nD) – (nA + nB)
= (2 + 3) – (3 + 2) = 0
2KClO3(s) ⟶ 2KCl(s) + 3O2(g) ∆n = (nKCl + nO2) - (nKClO3)
=(0 + 3)–(0)=3
(We take the n of KClO3 and KCl az «zero» since they are solid)
2H2O2(l) ⟶ 2H2O(l) + O2(g) ∆n = 1
NO(g) + O3(g) ⟶ NO2(g) + O2(g) ∆n = (1+1)-(1+1)=0
2C2H6(g) + 7O2(g) ⟶ 4CO2(g) + 6H2O(l) ∆n = 4 – (2+7) = -5
4NH3(g) + 5O2(g) ⟶ 4NO(g) + 6H2O(g) ∆n = (4+6) –(4+5) = 1
22
Exercise question:
Calculate the work done by the following reaction if 5.0 moles of carbon dioxide
reacts in the presence of excess water at 1 atm presure and 25 °C:
CO2(g) + 2H2O(l) ⟶ CH4(g) + 2O2(g)
Hints: w = - P ∆V = - ∆nRT, Ans: -24.776 kJ

23
Exercise question:
Given the thermochemical equation
2SO2(g) + O2(g) ⟶ 2SO3(g), ∆H°rxn= –198 kJ
Calculate the work if 6.5 moles of SO2 reacts at 90 °C at a constant pressure.
Ans: +9.81 kJ

24
 A Comparison of DH and DU

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

DU = DH - PDV At 25 oC, 1 mole H2 = 24.5 L at 1 atm
PDV = 1 atm x 24.5 L = 2.5 kJ
DU = -367.5 kJ/mol – 2.5 kJ/mol = -370.0 kJ/mol
Hence,
DU (-370.0 kJ/mol) is very close to DH (-367.5 kJ/mol)
Therefore,
Heat changes (q or DH) are more effective
than work (w) in changing the energy (DU) of
most systems

25
Exercise question:
Calculate the enthalpy (∆H) and internal energy (∆U), in kilojoules, when 3.0 moles
of ethylene reacts with excess oxygen at 1 atm and 20 °C according to the
thermochemical equation:
C2H4(g) + 3O2(g) ⟶ 2CO2(g) + H2O(l) ∆H°rxn= –1411 kJ
Hints: ∆U = ∆H - P ∆V = ∆H - ∆nRT, ∆n = -2 (why?) Ans: ∆H = - 4233 kJ, ∆U = - 4218 kJ

26
Exercise question:
Calculate the enthalpy (∆H) and internal energy (∆U), in kJ, when 72.9 g of
magnesium reacts with excess oxygen at 1 atm and 25 °C if
2Mg(s) + O2(g) ⟶ 2MgO(s), ∆H° = –1203.6 kJ
Ans: ∆H = - 1805.4 kJ, ∆U = - 1801.6 kJ

27
Calorimetry :
Measurement of heat changes

Calorimeter:
An isolated/closed container to measure heat
changes

28
 Specific Heat and Heat Capacity
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

Table 6.2 The Specific Heats of
Some Common Substances
amount of heat (q) required to raise the
temperature of a given quantity (m) of the
Specific Heat substance by one degree Celsius.
Substances
 J g. C 
o

AI 0.900 C =ms
Au 0.129
C  graphics  0.720 Heat (q) absorbed or released:
C  diamond  0.502
Cu 0.385 q = m  s  Δt
Fe 0.444
q = C  Δt
Hg 0.139
Pb 0.158 Δt = t final – tinitial
H2O 0.184
C2H2OH  ethanol  2.46
© McGraw-Hill Education. 6-29
Example (6.7): A 466-g sample of water is heated from 8.50C to 74.60C.
Calculate the amount of heat absorbed (in kilojoules) by the water.

Ans:129KJ
 Constant-Volume Calorimetry

qsys = qwater + qbomb + qrxn

qsys = 0
qrxn = –  qwater + qbomb 
qwater = m × s × Δt
qbomb = Cbomb × Δt

Reaction at Constant V

ΔH  qrxn
No heat enters or leaves!
ΔH ~ qrxn

© McGraw-Hill Education. 6-31

 Example 6.8 (1 of 3)
A quantity of 1.435 g of naphthalene  C10H8  ,
pungent-smelling substance used in moth
repellents, was burned in a constant-
volume bomb calorimeter.

Consequently, the temperature of the water

rose from 20.28 C to 25.95C.

C10H8
If the heat capacity of the bomb plus water
was 10.17 kJ o C,
calculate the heat of combustion of
naphthalene on a molar basis; that is, find
the molar heat of combustion.

© McGraw-Hill Education. 6-32

 Example 6.8 (2 of 3)
Solution
The heat absorbed by the bomb and water is equal to the product of the
heat capacity and the temperature change.
assuming no heat is lost to the surroundings, we write

qcal = Ccal Δt
= 10.17KJ C  25.95 C – 20.28 C 
= 57.66 kJ

Because qsys = qcal + qrxn = 0, qcal = – qrxn .

The heat change of the reaction is −57.66 kJ. This is the heat released
by the combustion of 1.435 g of C10H8; therefore, we can write the
conversion factor as
– 57.66 kJ
1.435 g C10H8
© McGraw-Hill Education. 6-33
 Example 6.8 (3 of 3)

The molar mass of naphthalene is 128.2 g, so the heat of

combustion of 1 mole of naphthalene is

– 57.66 kJ 128.2 g C10H8

molar heat of combustion = ×
1.435 g C10H8 1 mol C10H8
= – 5.151× 103 kJ mol

Check
Knowing that the combustion reaction is exothermic and that the
molar mass of naphthalene is much greater than 1.4 g, is the
answer reasonable? Under the reaction conditions, can the heat
change (257.66 kJ) be equated to the enthalpy change of the
reaction?
© McGraw-Hill Education. 6-34
Example 6.9: It has been suggested that hydrogen gas obtained by the
decomposition of water might be a substitute for natural gas (principally methane).
To compare the energies of combustion of these fuels, the following experiment
was carried out using a bomb calorimeter with a heat capacity of 11.3 kJ/C. When
a 1.50-g sample of methane gas was burned with excess oxygen in the
calorimeter, the temperature increased by 7.3C. When a 1.15-g sample of
hydrogen gas was burned with excess oxygen, the temperature increase was
14.3C. Compare the energies of combustion (per gram) for hydrogen and
methane.
Ans: methane 55KJ/g, H2 141KJ/g; The energy released in the combustion of 1 g hydrogen is approximately 2.5 times that for 1 g
methane, indicating that hydrogen gas is a potentially useful fuel.
 Constant-Pressure Calorimetry

qsys = qwater + qcal + qrxn

qsys = 0
qrxn = –  qwater + qcal 
qwater = m × s × Δt
qcal = Ccal × Δt

Reaction at Constant P
ΔH = qrxn
No heat enters or leaves!

© McGraw-Hill Education. 6-36

 Example 6.10 (1 of 3)

A lead (Pb) pellet having a mass

of 26.47 g at 89.98 C was
placed in a constant-pressure
calorimeter of negligible heat
capacity containing 100.0 mL of
water.

The water temperature rose

from 25.50 C to 23.17 C.

What is the specific heat of the

lead pellet?

© McGraw-Hill Education. 6-37

 Example 6.10 (2 of 3)

Solution
Treating the calorimeter as an isolated system (no heat lost to
the surroundings), we write
qPb + qH2 O = 0
or
qPb = – qH2O
The heat gained by the water is given by

qH2O = ms Δ t

where m and s are the mass and specific heat and

Δt = t final – tinitial

© McGraw-Hill Education. 6-38

 Example 6.10 (3 of 3)

Therefore,

qH2O = 100.0 g  4.184J g  C   23.17 C – 22.50 C 

= 280.3 J

Because the heat lost by the lead pellet is equal to the heat
gained by the water, qPb = −280.3 J. Solving for the specific
heat of Pb, we write
qPb = msΔt
– 280.3 J =  26.47g   s   23.17 C – 89.98 C 
s = 0.158J g  C

© McGraw-Hill Education. 6-39

Example 6.11: When 1.00 L of 1.00 M Ba(NO3)2 solution at 25.0°C is mixed with
1.00 L of 1.00 M Na2SO4 solution at 25.0°C in a calorimeter, the white solid BaSO4
forms, and the temperature of the mixture increases to 28.1°C. Assuming that the
calorimeter absorbs only a negligible quantity of heat, that the specific heat
capacity of the solution is 4.18 J/°C . g, and that the density of the final solution is
1.0 g/mL, calculate the enthalpy change per mole of BaSO4 formed.
Ans: ΔH =-2.6 104 J/mol =-26 kJ/mol
Exercise question:
An iron cube weighing 15.5 g at 125.3 °C was placed in a constant-pressure
calorimeter of negligible heat capacity containing 100.0 mL of water at 25.1°C.
What is the final temperature of iron and water after equilibration of temperature?
(Assume that Ccal = 0 J/°C)
Hints: negligible heat capacity means Ccal ≈ 0 J / g.°C , so qCal = 0 , sFe=0.444 J/g.°C, sH2O=4.184 J/g.°C Ans: 26.8 °C,

41
 Enthalpy of Formation

Because there is no way to measure the absolute value of the

enthalpy of a substance, must I measure the enthalpy change for
every reaction of interest?
Establish an arbitrary scale with the standard enthalpy of formation ΔH f0  
as a reference point for all enthalpy expressions.
Standard enthalpy of formationΔH f0 
is the heat change 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.
ΔH f0  O2  = 0 ΔH f0  C,graphite  = 0
ΔH f0  O3  = 142 KJ mol ΔH f0  C,diamond = 1.90 KJ mol

© McGraw-Hill Education. 6-42

Some Standard Enthalpies of Formation

© McGraw-Hill Education. 6-43

 Enthalpy of Reaction

The standard enthalpy of reaction  ΔHrxn

0

is the enthalpy of a reaction carried out at 1 atm.
aA + bB  cC + dD

0
ΔHrxn = cΔHf0  C   dΔHf0 D   – aΔHf0  A  + dΔHf0 B  

0
ΔHrxn =  nΔHf0 products  –  mΔHf0 reactants 

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.)
© McGraw-Hill Education. 6-44
Using Enthalpy Diagrams to Calculate
∆H°

C  graphite  + 1 2O2  g   CO  g 
CO  g  + 1 2 O2  g   CO2  g 
C  graphite  + O2  g   CO2  g 

© McGraw-Hill Education. 6-45

 Example 6.12 (1 of 4)

Calculate the standard enthalpy of formation of acetylene

(C2H2) from its elements:
2C  graphite  + H2  g   C2H2  g 

The equations for each step and the corresponding enthalpy

changes are

 a  C  graphite  + O2  g   CO2  g  
ΔHrxn = – 393.5kJ / mol
1
b  H2  g  + O2  g   H2O  l  
ΔHrxn = – 285.8 kJ / mol
2
c  2C2H2  g  + 5O2  g   4CO2  g  + 2H2O  l  ΔHrxn

= – 2598.8kJ / mol

© McGraw-Hill Education. 6-46

 Example 6.12 (2 of 4)
Strategy
Our goal here is to calculate the enthalpy change for the formation of C2H2
from its elements C and H2. The reaction does not occur directly, however,
so we must use an indirect route using the information given by Equations
(a), (b), and (c).

Solution
Looking at the synthesis of C2H2, we need 2 moles of graphite as reactant.
So we multiply Equation (a) by 2 to get

 d 2C  graphite  + 2O2  g   2CO2  g  ΔHrxn


= 2  – 393.5 kJ / mol 
= – 787.0 kJ / mol

Next, we need 1 mole of H2 as a reactant and this is provided by Equation

(b). Last, we need 1 mole C2H2 of as a product.
© McGraw-Hill Education. 6-47
 Example 6.12 (3 of 4)

Equation (c) has 2 moles of C2H2 as a reactant so we need to

reverse the equation and divide it by 2:
5 1
e 2CO2  g  + H2O  l   C2H2  g  + O2  g  ΔHrxn

=  2598.8 kJ / mol 
2 2
= 1299.4 kJ / mol
Adding Equations (d), (b), and (e) together, we get

2C  graphite  + 2O2  g   2CO2  g  

ΔHrxn = – 787.0 kJ / mol
1
H2  g  + O2  g   H2O  l  
ΔHrxn = – 285.8 kJ / mol
2
5
2CO2  g  + H2O  l   C2H2  g  + O2  g  ΔHrxn

= 1299.4 kJ / mol
2
2C  graphite  + H2  g   C2H2  g  
ΔHrxn = 226.6 kJ / mol

© McGraw-Hill Education. 6-48

 Example 6.12 (4 of 4)

Therefore,
ΔH f = 226.6 kJ / mol

This value means that when 1mole of C2H2 is synthesized

from 2 moles of C(graphite) and 1mole of H2, 226.6 kJ of
heat are absorbed by the reacting system from the
surroundings. Thus, this is an endothermic process.

© McGraw-Hill Education. 6-49

Exercise question:
At 25°C, the following heats of reaction are known:
2ClF(g) + O2(g) ⟶ Cl2O(g) + F2O(g) ∆H°rxn = 167.4 kJ
2ClF3(g) + 2O2(g) ⟶ Cl2O(g) + 3F2O(g) ∆H°rxn = 341.4 kJ
2F2(g) + O2(g) ⟶ 2F2O(g) ∆H°rxn = –43.4 kJ

Use Hess's law to calculate ∆H°rxn for the reaction:

ClF(g) + F2(g) ⟶ ClF3(g)
Ans: –108.7 kJ

50
 Example 6.13 (1 of 4)

The thermite reaction involves

aluminum and iron(III) oxide

2Al  s  + Fe2O3  s   Al2O3  s  + 2Fe  l 

This reaction is highly exothermic

and the liquid iron formed is used to
weld metals.

Calculate the heat released in

The molten iron formed in a
per gram of Al reacted with thermite reaction is run
Fe2O3 . The ΔH f for Fe (l ) is 12.40 down into a mold between
the ends of two railroad
kJ / mol. rails. On cooling, the rails
are welded together.
© McGraw-Hill Education. 6-51
 Example 6.13 (2 of 4)
Strategy
The enthalpy of a reaction is the difference between the
sum of the enthalpies of the products and the sum of the
enthalpies of the reactants.

The enthalpy of each species (reactant or product) is

given by its stoichiometric coefficient times the standard
enthalpy of formation of the species.

© McGraw-Hill Education. 6-52

 Example 6.10 (3 of 4)
Solution
Using the given ΔH f value for Fe(l) and other


ΔHrxn =  ΔH f  Al2O3  + 2ΔH f  Fe   – 2ΔH f  Al  + ΔH f Fe2O3  
=  – 1669.8 kJ / mol  + 2 12.40kJ / mol   – 2  0  +  – 822.2kJ / mol  
= – 822.8 kJ / mol

This is the amount of heat released for two moles of Al reacted.

We use the following ratio
– 822.8 kJ
2 mol Al
to convert to kJ g Al.
© McGraw-Hill Education. 6-53
 Example 6.13 (4 of 4)

The molar mass of Al is 26.98 g, so

– 822.8 kJ 1 mol Al
heat released per gram of Al = ×
2 mol Al 26.98 g Al
= 15.25 kJ / g

Check
Is the negative sign consistent with the exothermic nature of
the reaction? As a quick check, we see that 2 moles of Al
weigh about 54 g and give off about 823 kJ of heat when
reacted with Fe2O3. Therefore, the heat given off per gram of
Al reacted is approximately – 830 kJ 54 g or – 15.4 kJ g.

© McGraw-Hill Education. 6-54

 Exercise question:
The enthalpy of combustion of acetylene C2H2 is described by
C2H2(g) + (5/2)O2(g) ⟶ 2CO2(g) + H2O(l) ∆H°rxn= –1299 kJ
Calculate the enthalpy of formation of acetylene, given the following enthalpies of
formation
∆H°f[CO2(g)] = –393.5 kJ/mol
∆H°f[H2O(l)] = –285.8 kJ/mol
Ans: +226 kJ/mol

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