General Chemistry II

Chapter 5
Thermochemistry

Dr. Laya Rajendran

 Thermochemistry
Energy Chemical
Change as Heat Reactions
Energy: Capacity to do work/transfer heat
Thermodynamics: Study of Energy and Energy
Transformation
Enthalpy
Heat of reaction
Heat of formation
Calorimetry
 Sections to be covered
1. The nature of energy

2. The 1st law of thermodynamics

3. Enthalpy
4. Enthalpies of reaction

5. Calorimetry
6. Hess’s law

7. Enthalpies of formation
1. The Nature of
Energy
1. The Nature of Energy
Kinetic Energy:
- Energy of motion (translational, rotational, vibrational)
- Depends on the mass of the body and its speed:
1
Ek = mv 2
2
Units: joule (J) 1 J = 1 N.m = kg m2/s 2

Potential Energy:
- Energy possessed by an object as a result of its position
- Mainly due to gravity, which depends on the mass of the object
and its height from a certain reference point:
Ep = mgh
1. The Nature of Energy
Electrostatic Potential Energy:
- A type of potential energy
- Mainly between charged particles

Eel = kQ1 Q2 Where

Q1 & Q2 are the charges
d d is the distance between them
k is a constant = 8.99 x 109 J.m/C2
Note:
1. If Q1 and Q2 have opposite charges,
Eel is the force of attraction between them

2. If Q1 and Q2 have same charges,

Eel is the force of repulsion between them
1. The Nature of Energy
Units of energy:
SI unit of energy is the joule (J)

1 J = 1 kg.m2/s2
Note: calorie (cal) is another unit of energy, where:
1 cal = 4.184 J
1 Cal = 1 kcal = 1000 cal
Definition:
1 cal = amount of energy required to raise the temperature
of 1 g of water from 14.5oC to 15.5oC.
1. The Nature of Energy
System and Surroundings: Universe
System: part of the universe we are interested in
(under study).
Surroundings: the rest of the universe
System:
(Closed, Open, Isolated)
Exchange of energy and/or
matter. system

surroundings
 1. The Nature of Energy
Work: The product of force applied to an object over a
distance.
w =F d
W = - P ext. ΔV
Work of expansion into a vacuum?

Energy: The work done to move an object against a force

Heat: The transfer of energy between two objects (hotter to colder)
Internal energy (E):
The total (kinetic + potential) energy of all components in a system,
where DE = Efinal - Einitial
(since absolute E can not be measured)
2. The First Law of
Thermodynamics
2. The First Law of Thermodynamics
“Energy is conserved”
This means that energy of (system + surroundings) is CONSTANT.
DE universe = zero
DE system + DE surrounding = zero

i.e. any energy transferred from a system must be transferred to

the surroundings (and vice versa).
When a system undergoes a physical or chemical change, the change
in internal energy is given by the heat added to or absorbed by the
system plus the work done on or by the system:

DE = q + w
2. The 1st law of Thermodynamics
DE = q + w
q is positive
when heat is absorbed by the
system
w is positive
when work is done on the system

q is negative
when heat is released by the system
w is negative
when work is done by the system
2. The 1st law of Thermodynamics
2. The 1st law of Thermodynamics
Endothermic vs. Exothermic processes

If heat is absorbed by the system

i.e. absorbed from the surroundings
Endothermic process

If heat is released by the system

i.e. transferred to the surroundings
Exothermic process
2. The 1st law of Thermodynamics
State Functions vs. Path Functions
State: Functions that depends on the current status of the system
not how it got there (independent of the path).
Path: Dependent on the path. Δ can only be used with state functions.
ΔE = Efinal – Einitial
w and q?
2. The First Law of Thermodynamics

Example 2:
DE of discharging a flash light at a constant temperature

DE
( as a state function)
is the same
in both cases
3. Enthalpy
(H)
 3. Enthalpy (H)
As a result of chemical reactions, heat and/or work can be done
Example:
Zn(s) + 2H+(aq)  Zn2+(aq) + H2(g) @a
constant pressure

w = - P DV
The increase in
volume is done to
keep the internal
pressure constant
3. Enthalpy (H)
At a constant pressure
H is the heat transferred between the system and surroundings
Where: H = E + PV
i.e. DH = DE + PDV
H is also a “state function”, which does not depend on the route/pathway
by which reaction takes place, as long as pressure is constant.
Since DE
=q+w & w = -PDV
DH = qp + PDV – PDV = qp Constant pressure

i.e. the change in enthalpy is therefore equal to the heat gained or lost
at a constant pressure
3. Enthalpy
DH = qp

qp is +ve qp is -ve

In a chemical reaction,
DH = Hfinal – Hinitial
= Hproducts - Hreactants
4. Enthalpies of
Reactions
4. Enthalpies of Reactions
Example:
CH4(g) + 2O2(g)  CO2(g) + 2H2O(l) DH = -890 kJ

Rules of DH:
1. DH is an “extensive property”, i.e. directly proportional to the
amount of reactant consumed in the process:

Example:
CH4(g) + 2O2(g)  CO2(g) + 2H2O(l) DH = - 890 kJ
x2
2CH4(g) + 4O2(g)  2CO2(g) + 4H2O(l) DH = -1780kJ
4. Enthalpies of Reactions
Rules of DH:
2. DH of a reaction is equal in magnitude but opposite in sign to DH of
the opposite reaction:
Example:
CH4(g) + 2O2(g)  CO2(g) + 2H2O(l) DH = -890 kJ
CO2(g) + 2H2O(g)  CH4(g) + 2O2(l) DH = +890 kJ

3. DH of a reaction depends on the state of the reactants and products

Example:
CH4(g) + 2O2(g)  CO2(g) + 2H2O(l) DH = -890 kJ
CH4(g) + 2O2(g)  CO2(g) + 2H2O(g) DH = -802 kJ

Why? 2H2O(l) 2H2O(g) DH = +88 kJ

4. Enthalpies of Reactions
Practice Exercise:
H2O2 can decompose to water and oxygen by the following reaction:
2H2O2 (l) 2H2O (l) + O2 (g) DH = -196 kJ
Calculate the value of q when 5.00 g of H2O2 (l) decomposes at a
constant pressure.
5. Calorimetry
5. Calorimetry
It is the measure of heat flow using a calorimeter using the
parameter “Heat capacity”
Heat Capacity:
is the amount of heat required by an object to raise its temperature
by 1 K or 1 oC (extensive property)

Molar heat capacity

(of 1 mol of a substance) (intensive)

Specific heat capacity (also called: Specific Heat)

(of 1 g of a substance) (intensive)
Note:
Molar heat capacity = (specific heat capacity) x (formula weight)
Example:
Molar heat capacity of H2O = (4.18 J/g-K) x (18.0 g/mol) = 75.2 J/mol-K
5. Calorimetry
Quantity of heat transferred
Specific heat =
grams of substance x temperature change
q
=
m x DT
i.e.
q = (specific heat) x (grams of substance) x DT
Example:
If 209 J is required to increase the temperature of 50.0 g of water by
1.00 degree K, then the specific heat of water is:
209 J
= 4.18 J/g-K
50.0 g x 1.00 K
Note:
DT can be in K or oC, since both are equal in magnitude
5. Calorimetry
Types of calorimeters

Constant-pressure Constant-volume
5. Calorimetry
Constant-pressure calorimeter
Heat released/absorbed is qp = DH

Remember:
If DH is +ve endothermic
If DH is –ve exothermic

In exothermic reactions, heat released

by the reaction is absorbed by solution

i.e. qrxn = - qsol = -[(specific heat of solution) x (grams of solution) x DT]

Note:
In dilute solutions, specific heat of solution = specific heat of water
5. Calorimetry
Constant-pressure calorimeter
Practice Exercise:
When 50ml of 0.1 M AgNO3 and 50ml of 0.1M HCl are mixed in a
constant-pressure calorimeter, the temperature of the mixture increases
from 22.3oC to 23.11oC, caused by the following reaction:
AgNO3 (aq) + HCl (aq) AgCl (s) + HNO3 (aq)
Calculate DH for this reaction, assuming that the combined solution has
a mass of 100 g and a Specific heat of 4.18 J/g-oC

Solution
In Class !!!
5. Calorimetry
Constant-volume calorimeter
(Bomb Calorimetry)

Here, reaction is carried out under a

constant volume.

Usually used to study combustion.

Using it is based on the knowledge

of the calorimeter heat capacity (Ccal).
Then
qrxn = - Ccal x DT
5. Calorimetry
Constant-volume calorimeter
Practice Exercise:
A 0.5865 g sample of lactic acid (HC3H5O3) is burned in a calorimeter
whose heat capacity is 4.1812 kJ/oC. The temperature increases from
23.1oC to 24.95 oC. Calculate the heat of combustion of lactic acid
per gram and per mole of lactic acid.

Solution
In Class !!!
6. Hess’s Law
6. Hess’s Law
“If a reaction is carried out in a number of steps, DH for the
overall reaction is the sum of DH for each individual step.”
Example 1:
CH4(g) + 2O2(g)  CO2(g) + 2H2O(g) DH = -802 kJ
2H2O(g)  2H2O(l) DH = -88 kJ
CH4(g) + 2O2(g)  CO2(g) + 2H2O(l) DH = -890 kJ
6. Hess’s Law
“If a reaction is carried out in a number of steps, DH for the
overall reaction is the sum of DH for each individual step.”
Example 2:
Note that:
DH1 = DH2 + DH3
 6. Hess’s Law
Practice Exercise:
C occurs in 2 forms: graphite and diamond. The enthalpy of
combustion of graphite is -393.5 kJ/mol and that of diamond is
-395.4 kJ/mol. Calculate DH for the conversion of graphite to diamond.

Solution
In Class !!!
7. Enthalpies of
Formation
(DHf)
7. Enthalpies of Formation (DHf)
If 1 mol of compound is formed from its constituent elements,
then the enthalpy change for this reaction is called the
“enthalpy (or heat) of formation”, DHf

Example:
C (s) + O2 (g) CO2 (g), DHf = -395.4 kJ/mol

If 1 mol of compound is formed from substances in their “standard

states”, then the enthalpy change is called
“Standard enthalpy (or heat) of formation”, DHof

Where:
Standard conditions (states) are: 1 atm and 25oC (298 K).
7. Enthalpies of Formation (DHf)
7. Enthalpies of Formation
Notes:
1. If there is more than one state for a substance under standard
conditions, the more stable one is used.

2. Standard enthalpy of formation of the most stable form of

an
element is zero.
3. We use Hess’ Law to calculate enthalpies of a reaction from
enthalpies of formation.

° =  n D Hf° (products) - m D Hf° (reactants)

DHrxn
7. Enthalpies of Formation
Example:
C3H8 (g) + 5O2 (g) 3CO2 (g) + 4H2O (l)
What is DHrxn ?

Solution
in class !!!
7. Enthalpies of Formation
Practice Exercise:
Given the following standard enthalpy of rxn, use the standard
enthalpies of formation in Table 5.3 to calculate the standard enthalpy
of formation of CuO (s)
CuO (s) + H2 (g) Cu (s) + H2O (l), DHo = -129.7 kJ

Solution
in class !!!
7. Enthalpies of Formation
Typical Exam Question (Fall 2003):
Use the enthalpies of the following reactions to calculate DH for the
reaction of ethylene with F2
H2(g) + F2(g) 2HF(g) DH=-537 kJ
C(s) + 2F2 (g) CF4 (g) DH=-680 kJ
2C(s) +2H2 (g) C2H4(g) DH=+52.3 kJ

C2H4(g) + 6 F2(g) 2 CF4(g) + 4HF (g)

Solution
in class !!!
 End
of
Chapter 5
Thermochemistry