Department of Chemistry

General Chemistry for Health Sciences

10231114

Chapter 6

Thermochemistry
Fall, 2023/2024
 Outline

➢ 6.1 The Nature of Energy and Types of Energy

➢ 6.2 Energy Changes in Chemical Reactions
➢ 6.3 Introduction to Thermodynamics
➢ 6.4 Enthalpy of Chemical Reactions
➢ 6.5 Calorimetry
➢ 6.6 Standard Enthalpy of Formation and Reaction

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 Warning
This supplementary material should not be construed as a substitute for the
prescribed textbook or serve as a comprehensive course reference. The
primary and recommended reference for this course is:

.‫هذا المواد التكميلية ال تستبدل بأي شكل من األشكال الكتاب المقرر أو تمثل مرجعا لهذا المساق‬
:‫المرجع الرئيسي والمستحسن لهذه الدورة هو كتاب الكيمياء بالعنوان التالي‬

Title: Chemistry Authors: Jason Overby & Raymond Chang Edition: 12th
Edition

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 Energy Sources
Renewable Energy
Such as water, wind, solar (sun), hydrogen

Non-renewable Energy
Such as petroleum

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 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
Work direct energy change accompany a certain process
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 6.2 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 = Thermal Energy

Note that:
25oC = 298 Kelvin (K)
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Thermochemistry is the study of heat change in chemical
reactions.
 universe

surrounding
system
The system is the specific part of the universe that is of
interest in the study.

open closed isolated

Exchange: mass & energy energy nothing 8
 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 combination

H2O (g) H2O (l) + energy condensation

H2O (l) H2O (s) + energy freezing

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) dissociation

energy + H2O (s) H2O (l) melting

energy + H2O (l) H2O (g) vaporization
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Schematic of Exothermic and Endothermic Processes

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 6.3 Introduction to Thermodynamics
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
Potential energy of hiker 1 and hiker 2
is the same even though they took
different paths.
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First law of thermodynamics – energy can be
converted from one form to another, but cannot be
created or destroyed. DUuniverse = 0
DUsystem + DUsurroundings = 0
or
DUsystem = -DUsurroundings

C3H8 + 5O2 3CO2 + 4H2O

Exothermic chemical reaction!

Chemical energy lost by combustion = Energy gained by the surroundings

system surroundings

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 Another form of the first law for DUsystem
DU = q + w
DU 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

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 Work Done On the System
w=Fxd

w = -P DV
DV > 0
F
PxV= 2
x d3 = F x d = w -PDV < 0
d
wsys < 0

Work is
not a
state
function.
Dw = wfinal - winitial
initial final
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Example 6.1
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 and (b) against a constant pressure of 1.2 atm.

Similar problems: 6.15, 6.16. 15

Example 6.2
The work done when a gas is compressed in
a cylinder like that shown in Figure 6.5 is
462J.
During this process, there is a heat transfer
of 128 J from the gas to the surroundings. Figure 6.5 The compression
Calculate the energy change for this of a gas against a constant
process. (Given that: 1 L · atm = 101.3 J) external pressure

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Similar problems: 6.17, 6.18.
 Chemistry in Action: Making Snow

DU = q + w

Adiabatic process (very quick)

q=0

w < 0, DU < 0

DU = CDT

DT < 0, SNOW!

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Chemistry in Action: Inflating a bicycle /car tire
DU = q + w
Adiabatic process
(very quick)

q=0

w > 0, DU > 0

DU = CDT
DT > 0, Warming!

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 6.4 Enthalpy (H) of Chemical Reactions
Enthalpy (H) is used to quantify the heat (q) flow into or out of
a system in a process that occurs at constant pressure.
DH = H (products) – H (reactants)
DH = heat given off or absorbed during a reaction at constant pressure

product reactant

reactant product

Hproducts > Hreactants Hproducts < Hreactants

DH > 0 Endo. DH < 0 Exo. 19
 Thermochemical Equations
CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (l) DH = - 890.4 kJ/mol
DH negative
System gives off heat
Exothermic reaction
890.4 kJ are released for every 1 mole of methane
that is combusted at 250C and 1 atm.

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

DH positive
System absorbs heat
Endothermic reaction
6.01 kJ are absorbed for every 1 mole of ice that melts
at 00C and 1 atm.
Dr. Mohammed Suleiman Shtaya 20
 Thermochemical Equations

• The stoichiometric coefficients always refer to the number

of moles of a substance
H2O (s) H2O (l) DH = 6.01 kJ/mol

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

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.

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

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 Thermochemical Equations

• The physical states of all reactants and products must be

specified in thermochemical equations.
H2O (s) H2O (l) DH = 6.01 kJ/mol
H2O (l) H2O (g) DH = 44.0 kJ/mol

Important note:
At constant pressure heat q = qp = DH

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Example 6.3
Given the thermochemical equation:
2SO2(g) + O2 (g) 2SO3(g) DH= - 198.2 kJ/mol
Calculate the heat evolved when 87.9 g of SO2(g) (molar mass =
64.07 g/mol) is converted to SO3 (g).

Similar problem: 6.26. 23

 A Comparison of DH and DE
Enthalpy( H) and the First Law of Thermodynamics
H = U +p V DU = q + w

At constant pressure: q = DH and w = -PDV

DU = DH - PDV
DH = DU + PDV or DH = DU + Dn RT
Note : PDV = Dn RT
R =8.314 J /mol. K
Dn= sum n gas product –sum n gas reactant

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Dr. Mohammed Suleiman Shtaya
 A Comparison of DH and DE
Example:
Consider the reaction :
2Na (s) + 2H2O (l) 2NaOH (aq) + H2 (g) DH = -367.5 kJ/mol
At 25 oC, and 1 atm. Find DU. (given that R =0.082 L. atm /mol. K)
Solution:
T = 25oC = 273+25 = 298 K
1mol H2 gas at 298K and 1 atm equal to 24.5 L

DU = DH - PDV
PDV = 1 atm x 24.5 L = 24.5 L . atm = 2.5 kJ
DU = -367.5 kJ/mol – 2.5 kJ/mol = -370.0 kJ/mol

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 A Comparison of DH and DE
Example:
Consider the reaction :
2Na (s) + 2H2O (l) 2NaOH (aq) + H2 (g) DH = -367.5 kJ/mol
that occur at 25oC, find DU? (given that R =8.314 J /mol. K)

Solution:
T = 25oC = 273+25 = 298 K
Dn = 1-0 =1 mol gas
DH = DU + Dn RT
DU = DH - Dn RT
DU = -367.5 kJ – 1*8.314*10-3*298 = -370kJ / mol

Dr. Mohammed Suleiman Shtaya 26

Example 6.4
Calculate the change in internal energy when 2 moles of CO are
converted to 2 moles of CO2 at 1 atm and 25°C:

(given that R =8.314 J /mol. K)

Similar problem: 6.27. 27

Dn = 0 No expansion work DH = DE
No work is done by the system or on the system

2Na (s) + 2H2O (l) 2NaOH (aq) + H2 (g)

Dn > 0 expansion work |DH| < |DE|

Work is done by the system on the surrounding

2N2 (g) + 3H2 (g) 2 NH3 (g)

Dn < 0 compression work |DH | > |DE|

Work is done by the surrounding on the system

Dr. Mohammed Suleiman Shtaya 28

 6.5 Calorimetry
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 - Tnitial

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Example 6.5
A 466g sample of water is heated from 8.50°C to 74.60°C.
Calculate the amount of heat absorbed (in kilojoules) by the water.

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Similar problem: 6.33.
 Constant-Volume Calorimetry

qsys = qwater + qbomb + qrxn

qsys = 0
qrxn = - (qwater + qbomb)
qwater = m x s x Dt
qbomb = Cbomb x Dt

Reaction at Constant V
DH = qrxn
DH ~ qrxn
No heat enters or leaves! 31
 Example 6.6
A quantity of 1.435 g of naphthalene (C10H8), a 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.
If the heat capacity of the bomb plus water was 10.17 kJ/°C,
calculate the heat of combustion of naphthalene on a molar basis; that is, find
the molar heat of combustion.

C10 H8

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Similar problem: 6.37.
 Constant-Pressure Calorimetry

qsys = qwater + qcal + qrxn

qsys = 0
qrxn = - (qwater + qcal)
qwater = m x s x Dt
qcal = Ccal x Dt

Reaction at Constant P
DH = qrxn

No heat enters or leaves! 33

Example 6.7
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?

Similar problem: 6.88. 34

Example 6.8
A quantity of 1x102 mL of 0.500 M HCl was mixed with1x102 mL of 0.500M
NaOH in a constant-pressure calorimeter of negligible heat capacity.
The initial temperature of the HCl and NaOH solutions was the same,
22.50 C, and the final temperature of the mixed solution was 25.86 C.
Calculate the heat change for the neutralization reaction on a molar basis:
NaOH ( aq ) + HCl ( aq ) → NaCl ( aq ) + H 2 O ( l )
Assume that the densities and specific heats of the solutions are the same
as for water (1.00 g/ mL and 4.184 J/g∙°C, respectively)

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Similar problem: 6.38.
36
 Chemistry in Action:
Fuel Values of Foods and Other Substances
More in self reading
C6H12O6 (s) + 6O2 (g) 6CO2 (g) + 6H2O (l) DH = -2801 kJ/mol

1 cal = 4.184 J
1 Cal = 1000 cal = 4184 J

Substance DHcombustion (kJ/g)

Apple -2

Beef -8

Milk -3

Gasoline -34 37
How to Calculate the change in the enthalpy of reaction DH
1) The standard enthalpy of reaction (DH0rxn) is the enthalpy
of 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)

2) 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.)
Dr. Mohammed Suleiman Shtaya 38
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 (DH0f ) as a reference point for all enthalpy
expressions.

Standard enthalpy of formation (DH0f) 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.
DH 0 (C, graphite) = 0
DH0f (O2) = 0 f

DH (O ) = 142 kJ/mol
0 DH 0 (C, diamond) = 1.90 kJ/mol
f
f 3 39
40
Using enthalpies of formation DH0f , calculate the standard
change in enthalpy for the reaction:

Solution:

Dr. Mohammed Suleiman Shtaya 41

 Using the following reactions , calculate the standard change in
enthalpy for the reaction: C (graphite) + O2 (g) CO2 (g)

C (graphite) + 1/2O2 (g) CO (g) DH = -283 kJ for rxn 1

CO (g) + 1/2O2 (g) CO2 (g) DH = -110 kJ for rxn 2

C (graphite) + O2 (g) CO2 (g) DH = -393kJ for rxn (overall rxn)

Dr. Mohammed Suleiman Shtaya 42

How to Calculate the change in the enthalpy of reaction DH

DH = H (products) – H (reactants)
1)Using: The standard enthalpy of reaction (DH 0 ) is the
rxn
enthalpy of 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)

2) Using: Hesse's law

Dr. Mohammed Suleiman Shtaya 43

Calculate DH for C(graphite) + 2S(rhombic) 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

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

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Benzene (C6H6) burns in air to produce carbon dioxide and
liquid water. a) DHrxn given that:
DHf0 (O2) = 0 DHf0 (CO2) = - 393.5 kJ
DHf0 (C6H6) = 49.04 kJ DHf0 (H2O) = - 1187.64 kJ
Solution:
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–285.8 ] – [ 2x49.04 ] = -6535 kJ

b) How much heat is released per mole of benzene combusted?

-5946 kJ
= - 3267.5 kJ/mol C6H6
2 mol
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Dr. Mohammed Suleiman Shtaya
Calculate DH for the synthesis of diborane B2H6
from its elements, according to the equation

Dr. Mohammed Suleiman Shtaya 46

 DH for the above reaction = DHfo B2H6

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

DH = DHfo CS2

Dr. Mohammed Suleiman Shtaya 47

 Chemistry in Action: Bombardier Beetle Defense

C6H4(OH)2 (aq) + H2O2 (aq) C6H4O2 (aq) + 2H2O (l) DH0 = ?

C6H4(OH)2 (aq) C6H4O2 (aq) + H2 (g) DH0 = 177 kJ/mol

H2O2 (aq) H2O (l) + ½O2 (g) DH0 = -94.6 kJ/mol

H2 (g) + ½ O2 (g) H2O (l) DH0 = -286 kJ/mol

DH0 = 177 - 94.6 – 286 = -204 kJ/mol

Exothermic!

Dr. Mohammed Suleiman Shtaya 48

Review concepts and Practice Exercise

To be solved at home by each student

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Practice Exercise
A gas expands from 264 mL to 971 mL at constant temperature.
Calculate the work done (in joules) by the gas if it expands
(a) against a vacuum and
(b) against a constant pressure of 4.00 atm.

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 Practice Exercise
A gas expands and does P-V work on the surroundings equal to
279 J. At the same time, it absorbs 216 J of heat from the surroundings. What
is the change in energy of the system?

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Similar problems: 6.17, 6.18.
52
Practice Exercise
Calculate the heat evolved when 266 g of white phosphorus (P4)
burns in air according to the equation

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Similar problem: 6.26.
Practice Exercise

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Similar problem: 6.27.
55
Practice Exercise
An iron (Fe) bar of mass 869 g cools from 948C to 58C. Calculate the
heat released (in kilojoules) by the metal.

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 ‫‪self reading‬‬
‫‪Not tested‬‬
‫قراءة ذاتية‬
‫غير داخل في االمتحان‬

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CHEMISTRYY in Action self reading
White Fat Cells, Brown Fat Cells, and a Potential
Cure for Obesity

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