Thermochemistry

Chapter 6

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 Energy, nature & types
Energy is the capacity to do work. [work = force x distance]
Chemists define work as directed energy change resulting from a
process.
•Kinetic energy: the energy produced by moving object.
•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.
•Potential energy: is the energy available by virtue of an object’s position.
•Energy can be neither destroyed nor created.
Law of conservation of energy: the total quantity of energy in the
universe is assumed constant.
2
 Energy Changes in Chemical Reactions
Chemical reactions absorbs or release energy in the form of heat.
Heat is the transfer of thermal energy between
two bodies that are at different temperatures.
Temperature is a measure of the thermal energy.
“heat absorbed” or “heat released”
describe energy change during a process.

Temperature = Thermal Energy

(intensive) (extensive)

70oC
40oC Calorimeter Thermometer
greater temperature greater thermal energy 3
 Thermochemistry, System & Surrounding
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.
•The surroundings are the rest of the universe outside the
system.

Three
types of
systems

open closed isolated

Exchange: mass & energy energy nothing 4
 Exothermic and Endothermic Processes
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
 Thermodynamics & State function
Thermodynamics is the scientific study of the interconversion
of heat and other kinds of energy.
TD study changes in the state of a system, which is defined by
the values of all relevant macroscopic properties, e.g.,
composition, energy, temperature, pressure, and volume.
Energy, pressure, volume, and temperature are state function.
State functions are properties that are determined by the state
of the system, regardless of how that condition was achieved.

ΔV = Vf – Vi = 0.5 – 1.0
= – 0.5 L
ΔP = Pf – Pi = 200 – 100
= 100 mmHg
7
 Energy, a State function
The net increase in gravitational potential energy when
we go from the same starting point to the top of a mountain
is always the same, regardless of how we get there.

Energy, Pressure, Volume, Temperature

ΔE = Efinal – Einitial
ΔP = Pfinal - Pinitial
ΔV = Vfinal - Vinitial
ΔT = Tfinal - Tinitial
Gravitational Potential energy of hiker 1 and
hiker 2 is the same even though they took
different paths. 8
 First law of thermodynamics
Energy can be converted from one form to another,
but cannot be created or destroyed.
How do we know this is so?

Total energy content determination

is extremely difficult.
We measure the change in internal energy between initial
state and final state in a process.
ΔE = Efinal – Einitial
Internal energy = kinetic energy + potential energy
(molecular motion+ (attractive & repulsive interaction
movement of electrons) between electrons, nuclei &
molecules)
9
 First law of thermodynamics
It is impossible to measure all these contributions accurately,
so we cannot calculate the total energy of a system.
Changes in energy can be determined experimentally.
S(s) + O2(g) → SO2(g)
ΔE = E(product) – E(reactant)
Exothermic chemical reaction!
Chemical energy converted to thermal energy
Total energy of the universe is conserved
Sulfur burns in
air to form SO2. so the sum of energy change must be zero:
ΔEsystem + ΔEsurroundings = 0
or ΔEsystem = -ΔEsurroundings
Chemical energy lost by the = Thermal Energy gained by the
system surrounding 10
 Another form of the first law for ΔEsystem
ΔE = q + w
ΔE 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 = -PΔV when a gas expands against a constant external pressure

11
 Work Done by the System
Work, w = F x d (F = Force & d = distance)
w = -P ΔV (gas pushes piston up against atm. pressure P)

F ΔV > 0 Work done

P x V = 2 x d3 depend on P.
d -PΔV < 0 P = 0, w = 0
=Fxd=w wsys < 0 P = +ve, w = -PΔV

Work is
not a
state
function.
Δw = wfinal - winitial
initial final 12
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 ΔV

(a) ΔV = 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) ΔV = 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

101.3 J = -1430 J
w = -14.1 L•atm x
1L•atm
13
 Class Work – 6.14
Consider the changes,
a) Hg(l) → Hg(g) by the system on the surrounding

b) 3O2(g) → 2O3(g) by the surrounding on the system

c) H2(g) + F2(g) → 2HF(g) no work done

d) CuSO4⋅5H2O(s) → CuSO4(s) +
5H2O(g) by the system on the surrounding

At constant pressure, in which of the reaction is work

done by the system on the surrounding? By the
surrounding on the system? In which of them is no work
done?
14
 Heat, not a state function
Raising temperature of 100 g of water in
different way from 20oC to 30oC at 1 atm.
– Path 1: Bunsen burner, Δt = 10oC,
q = msΔt
= 100g×4.184J/g•oC×10oC = 4184 J
– Path 2: magnetic stirrer, Δt = 10oC,
q=0
– Path 3: Bunsen burner from 20 to 25oC,
stirrer from 25 to 30oC, Δt = 10oC,
q is in between 0 and 4184 J
• Heat change depends on how the process is carried
out, Δq = qf − qi
• q and w not state function but q + w = ΔE is a state
function
15
 Chemistry in Action: Making Snow

ΔE = q + w

q=0

w < 0, ΔE <
0
ΔE = CΔT

ΔT < 0,
SNOW!

16
 Class Work – 6.17
A gas expands and does P-V work on the
surroundings equal to 325 J. At the same time, it
absorbs 127 J of heat from the surroundings.
Calculate the change in energy of the gas.
Ans:

An expansion implies an increase in volume, therefore

w must be −325 J.
If the system absorbs heat, q must be +127 J. The
change in energy (internal energy) is:
ΔE = q + w = 127 J − 325 J = −198 J

17
 Internal Energy and the First Law of TD
How first law of TD can be applied to processes carried
out under different conditions.
Two situations most commonly encountered in the
laboratories:
▪ Volume of the system kept constant
▪ Pressure on the system kept constant
At constant volume:
ΔV = 0 and no P−V work; from 1st law
ΔE = q + w
= qv − PΔV
= qv

ΔE = qv
18
 Enthalpy and the First Law of TD
ΔE = q + w
At constant pressure: Enthalpy (H) a new function:
ΔE = q + w H = E + PV
= qp − PΔV ΔH = ΔE + Δ(PV), at const. P
qp = ΔE + PΔV ΔH = ΔE + PΔV
ΔH = qp

19
 Enthalpy of Reaction
Most reactions are constant-pressure process, so
heat change = enthalpy change
reactants → products
Enthalpy of reaction, ΔH, the difference between the
enthalpies of the products and the enthalpies of the reactants.
ΔH = H (products) – H (reactants)
ΔH = heat given off or absorbed during a reaction at constant pressure
ΔH > 0, positive, endothermic process, heat absorb by ‘sys’ from ‘surr’
ΔH < 0, negative, exothermic process, heat released by ‘sys’ to ‘surr’

Analogy for enthalpy ΔX = Xfinal – Xinitial

change to bank Tk.80 = Tk.180 – Tk.100 (deposit Tk.80)
account: – Tk.60 = Tk.40 – Tk.100 (withdraw Tk.60)
20
 Class Work – 6.28
Consider the reaction
H2(g) + Cl2(g) → 2HCl(g), ΔH = −184.6 kJ/mol
If 3 moles of H2 react with 3 moles of Cl2 to form HCl, calculate
the work done (in joules) against a pressure of 1.0 atm at
25oC. What is ΔE for this reaction? Assume the reaction
goes to completion.
Ans:
w = −PΔV and ΔE = ΔH − PΔV
3 moles of Cl2 and 3 moles of H2 gives 6 moles of HCl.
So, no volume change; ΔV = 0.
w = −PΔV = −(1 atm)(0 L) = 0
ΔE = ΔH − PΔV and −PΔV = 0, so ΔE = ΔH
ΔH = 3ΔHrxn = 3(−184.6 kJ/mol) = −553.8 kJ
ΔE = ΔH = −553.8 kJ
21
 Enthalpy Change in Physical Change

H2O(s) H2O(l) ΔH = 6.01 kJ/mol

6.01 kJ are absorbed for every 1 mole of ice that
melts at 00C and 1 atm.

Is ΔH negative or positive?
Hproducts > Hreactants
ΔH > 0
System absorbs heat
Endothermic Process

22
 Enthalpy Change in Chemical Change

CH4(g) + 2O2(g) CO2(g) + 2H2O(l) ΔH = -890.4 kJ/mol

890.4 kJ are released for every 1 mole of methane

that is combusted at 250C and 1 atm.

Is ΔH negative or positive?
Hproducts < Hreactants
ΔH < 0
System gives off heat
Exothermic Process

23
 Thermochemical Equations
Thermochemical equations, show the enthalpy changes as
well as the mass relationships.
H2O(s) H2O(l) ΔH = 6.01 kJ/mol

CH4(g) + 2O2(g) CO2(g) + 2H2O(l) ΔH = -890.4 kJ/mol

Guidelines for writing & interpreting:

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 ΔH changes:

H2O (l) H2O (s) ΔH = -6.01 kJ/mol
24
 Thermochemical Equations

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 x 6.01 = 12.0 kJ/mol

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

25
How much heat is evolved when 266 g of white phosphorus
(P4) burn in air?

P4 (s) + 5O2 (g) → P4O10 (s) ΔH = -3013 kJ/mol

1 mol P4 -3013 kJ
266 g P4 x x = -6470 kJ
123.9 g P4 1 mol P4

26
 Class Work – 6.19
Calculate the work done when 50.0 g of tin dissolves
in excess acide at 1.00 atm and 25oC:
Sn(s) + 2H+(aq) → Sn2+(aq) + H2(g)
Assume ideal gas behaviour.
Ans:

27
 Class Work – 6.25
In the industrial recovery of zinc, ZnS is converted to
ZnO by heating:
2ZnS(s) + 3O2(g) → 2ZnO(s) + 2SO2(g),
ΔH = −879 kJ/mol
Calculate the heat evolved (in kJ) per gram of ZnS.
Ans:
The equation as written shows that 879 kJ of heat is
released when two moles of ZnS react. We want to
calculate the amount of heat released when 1 g of ZnS
reacts.

28
 A Comparison of ΔH and ΔE

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

ΔE = ΔH - PΔV At 25 oC, 1 mole H2 = 24.5 L at 1 atm
PΔV = 1 atm x 24.5 L = 2.5 kJ
ΔE = -367.5 kJ/mol – 2.5 kJ/mol = -370.0 kJ/mol

29
 A Comparison of ΔH and ΔE
2Na(s) + 2H2O(l) 2NaOH(aq) + H2(g) ΔH = – 367.5 kJ/mol
ΔE = – 370.0 kJ/mol
• ΔE and ΔH are approximately same
• ΔH smaller than ΔE, some internal energy used to do
expansion work
• Reactions do not involve gases, ΔV is very small so ΔE
is practically same as ΔH
• For gaseous reactions ΔE can be calculated assuming
ideal behaviour:
ΔE = ΔH - Δ(PV)
= ΔH - Δ(nRT)
= ΔH - RTΔn
Δn = no. of moles of product – no. of moles of reactant
30
 Calorimetry: measurement of heat changes
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=mxsx
Δt
q = C x Δt
Δt = tfinal -
tinitial
31
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
Δt = tfinal – tinitial
= 5oC – 94oC = –89oC

q = msΔt

= 869 g x 0.444 J/g • oC x –89oC

= –34,000 J

32
 Class Work – 6.35

Calculate the amount of heat liberated (in kJ) from

366 g of mercury when it cools from 77.0oC to 12.0oC.
Specific heat of mercury, 0.139 J/g.oC.
Ans:

q = msΔt
= (366 g)(0.139 J/g·°C)(12.0°C − 77.0°C)
= −3.31 × 103 J
= −3.31 kJ

33
 Constant-Volume Calorimetry

qsys = qwater + qbomb + qrxn

qsys = 0
qrxn = - (qwater + qbomb)
qwater = m x s x
Δt
q =C x Δt
bomb bomb

Reaction at Constant V
ΔH = qrxn
ΔH ~ qrxn
No heat enters or leaves! 34
 Constant-Pressure Calorimetry

qsys = qwater + qcal + qrxn

qsys = 0
qrxn = - (qwater + qcal)
qwater = m x s x
Δt
q = C x Δt
cal cal

Reaction at Constant P
ΔH = qrxn

No heat enters or leaves! 35

36
 Chemistry in Action:
Fuel Values of Foods and Other Substances
C6H12O6 (s) + 6O2 (g) 6CO2 (g) + 6H2O (l) ΔH = -2801
kJ/mol
1 cal = 4.184 J
1 Cal = 1000 cal = 4184 J

Substance ΔHcombustion (kJ/g)

Apple -2

Beef -8

Butter -34

Gasoline -34 37
 Standard 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 (ΔHfo) as a reference point for all enthalpy
expressions.

Standard enthalpy of formation (ΔHfo) 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.
ΔHof (O2) = 0 ΔHof (C, graphite) = 0
ΔHof (O3) = 142 kJ/mol ΔHof (C, diamond) = 1.90 kJ/mol
38
39
 Standard Enthalpy of Reaction
o
The standard enthalpy of reaction (ΔHrxn ) is the enthalpy of
a reaction carried out at 1 atm.

aA + bB cC + dD

o
o
ΔHrxn = [ cΔHof (C) + dΔHof (D)] - [ aΔH f (A) + bΔHof (B)]
o
ΔHrxn = Σ nΔHof (products) - Σ mΔHfo (reactants)

To calculate ΔHorxn we must know ΔHof values of the

compounds that take place in the reaction.
These values can be determined by:
– The direct method
– The indirect method
40
 Standard Enthalpy of Reaction

• The direct method

For compounds that can be readily synthesized from
their elements in standard state:
C(graphite) + O2(g) → CO2(g) ΔHorxn = – 393.5 kJ/mol
ΔHorxn = ΔHof(CO2,g) – [ΔHof(C, graphite) + ΔHof(O2,g)]
= – 393.5 kJ/mol
ΔHorxn = ΔHof(CO2,g) = – 393.5 kJ/mol
ΔHof(CO2,g) = – 393.5 kJ/mol
Similarly,
S(rhombic) + 3F2(g) → SF6(g)
P4(white) + 5O2(g) → P4O10(s)
C(graphite) + 2S(rhombic) → CS2(l)

41
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)

o
ΔHrxn = Σ nΔHof (products) - Σ mΔHfo (reactants)

o
ΔHrxn = [ 12ΔHof (CO2)+ 6ΔHof (H2O)] - [ 2ΔHfo (C6H6)]
o
ΔHrxn = [ 12x–393.5 + 6x–187.6 ] – [ 2x49.04 ] = -5946 kJ

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

42
 Class Work – 6.51
Calculate the heat of decomposiiton for this process at
constant pressure and 25oC:
CaCO3(s) → CaO(s) + CO2(g)
Given, standard enthalpies of formations, CaCO3(s)
−1206.9; CaO(s) −635.6 and CO2(g) −393.5 kJ/mol,
respectively.
Ans:

43
 Standard Enthalpy of Reaction
• The indirect method
Many compounds can not be directly synthesized from
their elements,
– reaction does not go to completion
– reaction proceeds too slowly
– side reactions produce undesired products
ΔHof can be determined by indirect method based on
Hess’s law of heat summation

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.)
44
C(graphite) + O2(g) CO2(g)
CO(g) + 1/2O2(g) CO2(g)
C(graphite) + 1/2O2(g) CO(g) ?

C(graphite) + O2(g) CO2(g)

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

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

ΔHo f (CO) = − 393.5 + 283.0

= − 110.5 kJ/mol

45
Calculate the standard enthalpy of formation of CS 2(l) given
that:
o
C(graphite) + O2 (g) CO2 (g) ΔHrxn = -393.5
kJ/mol
S(rhombic) + O (g) SO (g) ΔHo = -296.1
2 2 rxn
kJ/mol
CS2(l) + 3O2 (g) CO2 (g) + 2SO2 (g) ΔHrxn o
= -1072
1. kJ/mol
Write the enthalpy of formation reaction for CS 2

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

2. Add the given rxns so that the result is the desired rxn.
o
C(graphite) + O2 (g) CO2 (g) ΔHrxn = -393.5
2SkJ/mol
(rhombic) + 2O2 (g) 2SO2 (g) ΔHrxn o
= -296.1 kJ/mol x
+2CO2(g) + 2SO2 (g) CS2 (l) + 3O2 (g) ΔHrxn o
= +1072
kJ/mol
C(graphite) + 2S(rhombic) CS2 (l)
o 46
ΔHrxn = -393.5 + (2x-296.1) + 1072 = 86.3 kJ/mol
 Chemistry in Action: Bombardier Beetle Defense

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

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

H2O2 (aq) → H2O (l) + ½O2 (g) ΔHo = -94.6 kJ/mol
H2 (g) + ½ O2 (g) → H2O (l) ΔHo = -286 kJ/mol

ΔHo = 177 - 94.6 – 286 = -204 kJ/mol

Exothermic!

47
 Heat of Solution
The heat of solution or enthalpy of solution (ΔHsoln) is the
heat generated or absorbed when a certain amount of solute
dissolves in a certain amount of solvent.

ΔHsoln = Hsoln - Hcomponents

Which substance(s) could be

used for melting ice?

Which substance(s) could be

used for a cold pack?

48
 Solution Process for NaCl

ΔHsoln = Step 1 + Step 2 = 788 – 784 = 4 kJ/mol 49

 Heat of Dilution
• When a solution is diluted, i.e., when more solvent is
added to lower the concentration, additional heat is
usually given off or absorbed.
• Heat of dilution or enthalpy of dilution is the heat
change associated with the dilution process.
• If a solution process is endothermic,
– when diluted more heat will be absorbed by the solution
• If a solution process is exothermic,
– when diluted more heat will be released by the solution
• Be cautious when working on a dilution procedure
• Dilution of con. H2SO4 is hazardous because of highly
exothermic heat of dilution
• “Add con. acid slowly to water.” (while constantly stirring)50
 Class Work – 6.64
Calculate the standard enthalpy change for the reaction
2Al(s) + Fe2O3(s) → 2Fe(s) + Al2O3(s)
given that
2Al(s) + 3/2O2(g) → Al2O3(s) ΔHorxn = − 1669.8 kJ/mol
2Fe(s) + 3/2O2(g) → Fe2O3(s) ΔHorxn = − 822.2 kJ/mol.
Ans:

51