Fall 2022

CHAPTER 6
Thermochemistry

1
Thermochemistry
• The study of the relationship between energy and chemistry

• Example: Hand warmers and instant cold packs

2
The Law of Conservation of Energy
Energy can be neither created nor destroyed. However, it
can be transferred from one object to another, and it can
assume different forms.

− In thermodynamics we are interested in the flow of energy,

particularly in the forms of heat and work.

− Heat and work describe the process of energy transfer

3
Definitions
• System
− The part of the universe we
chose to study

• Surroundings
− Everything with which the
system can exchange
energy

• Energy can be exchanged

between the two as heat and/or
work
4
Internal Energy

The internal energy (U) of a system is the sum of kinetic and

potential energies of all the particles that compose the
system.

A change in internal energy (ΔU):

ΔU = q + w
Where q is the heat transferred and w the work done

5
Internal Energy

ΔU = q + w
Where q is the heat transferred and w the work done.

6
Polling question
Consider a potato cannon which uses the ignition of a fuel to propel a potato a long
distance.

Consider the fuel and the molecules involved in combustion as the system.

If the burning of the fuel performs 800 J of work on the potato, and releases 1400 J
of energy as heat into the potato, what is ΔU of the fuel?

A) 2200 J
B) 600 J
C) -600 J
D) -2200 J
E) 0J

7
What is a State Function?

The internal energy is a state function. This

means that its value depends on the state
of the system not on how the system
arrived there (only the start and end
values are important)

Heat and work are not state functions. Their

values depend on the path the system
has taken from start to finish

8
Internal energy vs. Heat / Work
H2(g) + ½ O2(g) → H2O(l)

ΔrU = Uproducts - Ureactants

9
Temperature Changes and Heat Capacity

• In the case of a material that does not change phase, the increase in temperature
of a system ΔT due to the input of a given amount of heat q is given by

Heat (J) q = C ΔT Temperature change (ºC)

Heat capacity (J ºC-1)

• The heat capacity is a constant that depends on the mass and material of the
system
• Ex: one drop of water vs. a bucket of water

10
Temperature Changes and Heat Capacity
• Heat capacity is more useful when expressed
in terms of a given amount of a substance:

q = m Cs ΔT

• Cs is the specific heat capacity and can be used to

solve for q by plugging in the given mass

• Think about the physical meaning behind the Cs

value!

11
Polling question
When 100 g of water at 50°C is brought into contact with 100 g of methanol at
0°C the final temperature of both substances is 40°C.

What is the specific heat capacity of methanol relative to that of water?

A) Greater than Water

B) Less than Water
C) Exactly the same as water

12
Sign convention and conservation of energy

• When heat flows between a system and its surroundings, we define:

q to be positive if heat is supplied to the system (Tfinal > Tinitial)

q to be negative if heat is withdrawn from the system (Tfinal < Tinitial)

• Conservation of energy requires that

qsystem + qsurroundings = 0

qsystem = -qsurroundings

13
Let’s work a problem
A block of Cu has an initial temperature of 65.4°C. The Cu is immersed in a
beaker containing 95.7 g of H2O at 22.7°C. When the two substances reach
thermal equilibrium, the final temperature is 24.2°C. What is the mass of the Cu
block?

14
Work
• Often when a chemical reaction occurs, work is done in addition to heat transfer
(this is the principle of a car engine)

• Work is done when a force acts through a distance, many different “types” of
work possible

• In this course we will focus on pressure/volume (PV) work, only relevant for us
when gases are produced or consumed during a process

• Other types of work: spring compression/expansion work, electrical work

15
Pressure – Volume Work

16
Sign Convention - Pressure-Volume Work
• Similar sign conventions apply for work as for heat:
w is positive if work is done on the system by the surroundings (contraction of
gas, ΔV < 0)
w is negative if work is done by the system on the surroundings (expansion of
gas, ΔV > 0)

Example: If the air in a balloon expands from a volume of 0.100 L to 1.85 L against
a constant pressure of 1.00 bar, what is w with respect to the system?

17
Another way to calculate work
• Chemical reactions or other processes that produce or consume
gases result in work being performed

𝑤 = −𝑃Δ𝑉

But we know 𝑃𝑉 = 𝑛𝑅𝑇

If we assume temperature is constant (which we always will)

18
Let’s work a problem
Formic acid (CH2O2) is a liquid that burns in oxygen to produce gaseous CO2 and
liquid H2O. Compute the pressure-volume work (per mole of formic acid) at 298 K.
1
𝐶𝐻2 𝑂2 𝑙 + 𝑂2 𝑔 → 𝐶𝑂2 𝑔 + 𝐻2 𝑂 𝑙
2

19
Measuring ΔrU for Chemical Reactions
Most widely used apparatus is the bomb calorimeter,
Operates at constant volume

The reagents are the system and the calorimeter is

the surroundings

By measuring the heat transferred into the

surroundings ΔrU can be determined

X
20
Measuring ΔrU for Chemical Reactions
By measuring the heat transferred into the surroundings ΔrU can
be determined:

ΔU = qv + w

The temperature change (ΔT) can be measured and related to

the heat released by the system

qcal = Ccal x ΔT and qcal = - qr

qr = ΔU

What does the sign of ΔU tell us here?

21
Polling question
If the bomb calorimeter shows an increase in temperature, which of the
following statements is correct?

A) The internal energy of the products is less than the internal energy of the
reactants

B) ∆U > 0

C) Heat has been transferred from the surroundings to the system

D) q + w = 0
Let’s work a problem
When 1.010 g of sucrose (C12H22O11) undergoes combustion in a bomb calorimeter,
the temperature rises from 24.922 °C to 28.331 °C. Find ΔrU for the combustion
(per mole of sucrose). The heat capacity of the bomb calorimeter is 4.901 kJ °C-1

23
Let’s keep one thing clear
• Internal energy change ΔrU always applies for the reaction, even if
not performed at constant volume

• Bomb calorimeter (constant volume) just allows us to easily

determine ΔrU by relating it directly to heat of reaction q in that
particular experiment

24
Enthalpy
Enthalpy (H) is the heat evolved in a chemical reaction at constant
pressure and is a state function:

H = U + PV
ΔH = ΔU + PΔV

ΔH = qp

25
Polling question
Determine DH and DU for the reaction and conditions depicted below.
You shouldn’t need a calculator, use logic!

DH DU Vi= 0.120 m3 Vf= 0.110 m3

A) 250 kJ/mol 251 kJ/mol
B) 250 kJ/mol 249 kJ/mol
C) -250 kJ/mol -251 kJ/mol
D) -250 kJ/mol -249 kJ/mol
E) 250 kJ/mol -250 kJ/mol

Experiments show q = -250 kJ/mol and Vf < Vi

26
Determination of ΔrH from Bomb Calorimetry Experiments
Using a bomb calorimeter we can also determine the
enthalpy of reaction by finding ΔrU and converting to
ΔrH using a simple formula

Since ΔH = ΔU + PΔV and

PΔV = ΔnRT then

ΔrH = ΔrU + ΔnRT

27
Let’s keep one thing clear
• Enthalpy change ΔrH always applies for the reaction, even if not
performed at constant pressure

• Bomb calorimeter (constant volume) allows us to easily determine

ΔrU by relating it directly to heat of reaction q

• We then calculate ΔrH from ΔrU using the formula on previous slide

• The ΔrH value we calculated tells us what the heat of reaction would
be at constant pressure

28
Let’s work a problem
A 0.5224 g sample of C8H18 was combusted in a bomb calorimeter with a heat
capacity of 4.901 kJ °C-1. The temperature increased from 23.815 °C to 28.902 °C.
Determine ΔrH (per mole C8H18) for its complete combustion at 298 K.
Assume the products are gaseous CO2 and liquid H2O.

29
Exothermic and Endothermic Processes

ΔH is positive ΔH is negative

30
Constant-Pressure Calorimetry: Measuring ΔrH
• Coffee cup provides an insulated container for a
reaction to take place at constant pressure

• Heat absorbed by solution (usually water) in

calorimeter given by
qsurr = m x Cs x ΔT

• Heat of reaction is therefore:

q = -qsoln = ΔH

• ΔH value is usually divided by amount of reactant

(in mol), giving ΔrH in kJ/mol

31
Let’s work a problem
The following reaction is conducted in a coffee-cup calorimeter

Mg (s) + 2 HCl (aq) → MgCl2 (aq) + H2 (g)

0.158 g of Mg was reacted with excess HCl in water with a total volume of 100.0
mL. The temperature of the water rose from 25.6°C to 32.8°C. The Cs for water is
4.184 J g-1 °C-1. What is ΔrH for this reaction, per mol of Mg?

32
Relationship Involving ΔrH
1. If a chemical equation is multiplied by some factor, then ΔrH is also multiplied by
the same factor.

A + 2B → C ΔrH1
2A + 4B → 2C ΔrH2 =

2. If a chemical equation is reversed, then ΔrH change sign

A + 2B → C ΔrH1
C → A + 2B ΔrH2 =

33
Hess’s Law
The two relationships described on the previous
slide make it possible to determine the ΔrH for a
reaction without directly measuring it in the
laboratory.

For some reactions, direct measurements can be

difficult.

Example:

A + 2B → C ΔrH1 = 50 kJ/mol
C → 2D ΔrH2 = -100 kJ/mol

A + 2B → 2D Δ rH 3 =

34
Polling question
Given the following enthalpy data

A + B → 2C ∆rH1 = 25.0 kJ/mol

2E + F → C + D ∆rH2 = -50.0 kJ/mol

Predict ∆rH of the following reaction:

A + B + 2D → 4E + 2F

A) -25.0 kJ/mol
B) 25.0 kJ/mol
C) -125 kJ/mol
D) 125 kJ/mol
E) 0 kJ/mol
Let’s work a problem

36
Let’s work a problem

37
Determining ΔrHº from Standard Enthalpies of Formation
• The standard state
For a gas: the pure gas at a pressure of exactly 1 bar

For a Liquid or Solid: the pure substance in its most stable form at a pressure
of 1 bar and the temperature of interest (often will be 25 ºC).

For a Substance in Solution: The standard state for a substance in solution is

a concentration of exactly 1 mol L-1 (1 M).

• Standard enthalpy change (ΔrHº)

➢ The change in enthalpy for a process when all reactant and products are
in their standard states.

38
Determining ΔrHº from Standard Enthalpies of Formation

• Standard enthalpy of formation or standard heat of formation(ΔfHº)

For a compound: The change in enthalpy when 1 mol of the compound

forms from its constituent elements in their most stable forms at standard
state.

For a pure element in its most stable form at standard state:

ΔfHº = 0 kJ mol-1

• Examples of pure elements in their standard states:

39
Examples of standard enthalpies of formation

C (graphite) + ½ O2 (g) → CO (g) ΔHfo (CO(g)) = −110.5 kJ mol-1

½ H2 (g) + ½ F2 (g) → HF (g) ΔHfo (HF(g)) = −271.1 kJ mol-1

½ N2 (g) + ½ O2 (g) → NO (g) ΔHfo (NO(g)) = 90.25 kJ mol-1

40
Determining ΔrHº from Standard Enthalpies of Formation

41
Calculating ΔrHº
• Using the standard enthalpies of formation we can determine the standard
enthalpy change for a reaction:

ΔrHº = ∑ νpΔfHºproducts - ∑ νrΔfHºreactants

• Coefficients in the balanced chemical equation must be taken into account

42
Let’s work a problem

43
Let’s work a problem

44
Let’s work a problem

45
Polling question
The equations for the complete and incomplete combustion
of octane are given below.
DHf / kJ
25 mol-1
C8 H18 (l) + O2 (g) → 8CO2 (g) + 9H 2O(l)
2 CO -111
17
C8 H18 (l) + O2 (g) → 8CO(g) + 9H 2O(l)
2 CO2 -394

Which reaction is more exothermic? You shouldn’t

need a calculator!

A) Incomplete combustion

B) Complete combustion

46