ESci 115a – Chemistry

for Engineers
Mervin June B. Gasatan, RCh
Instructor I
Module 2
Chemical Thermodynamics
At the end of this discussion, the students will be able
to:
- Examine the basic concepts of thermodynamics and
one of its branches, thermochemistry.
- Learn how heat is measured in a calorimeter and how
the quantity of heat released or absorbed is related to
the amounts of substances involved in a reaction.
- Predict the direction of the spontaneous change, the
concept of free energy, and how it relates to the work
a system can do.
Lesson Overview

Definition of Terms

First Law of Thermodynamics

Calorimetry
I. Definition of Terms
Temperature vs Thermal Energy
Temperature – a measure of how hot or cold an object
is.
Thermal Energy – energy contained in an object
responsible for its temperature.

150 L 0.25 L
40°C 90°C
greater thermal lesser thermal
energy energy
Heat
- the transfer of thermal energy due to temperature
difference.
System vs. Surrounding
System – a specific part of the universe that we are
interested in.
Surrounding – everything that is not part of our
interest.
System Types
System Type Exchange of Exchange of
Matter? Energy?
Open System Yes Yes
Closed System No Yes
Isolated System No No
Endothermic Process
- the transfer of heat from the surrounding to system
(e.g. evaporation of water)
Exothermic Process
- the transfer of heat from the system to surrounding
(e.g. condensation of water)
Thermodynamics

Thermodynamics - the branch of

physical science that deals with the
relations between heat and other
forms of energy such as mechanical,
electrical, or chemical energy.
Thermochemistry - the quantitative
study of the relation between heat and
chemical reactions.
State vs. Path Function
Functions – properties that defines the system (energy,
temperature, work, etc.)
State Function – depends on the initial and final state of
the system.
Path Function – dependent on the path the system took.
State Function
height
Path Function
time
distance travelled
II. First Law of Thermodynamics
Law of Energy Conservation
(First Law of Thermodynamics)
Energy cannot be created nor destroyed but it is only
transformed from one form to the other.

q = heat exchange between system and surrounding

w = work done on (or by) the system
Sign Convention
Work: w
(Derivation)
Formula: w = -PΔV
Derivation:
(1) w = F x Δd w = F x Δd
(2) P = F/A w = (P*A) x ΔV/A
F=PxA w = PΔV
(3) ΔV = A x Δh w = -PΔV
Δh = ΔV/A
Practice!
A sample of methane gas
(CH4) expands in volume
from 2.0 L to 6.0 L at a
constant temperature.
Calculate the work done by
the CH4 if it expands against
(a) a vacuum and (b) a
constant pressure of 1.2
atm.
Solution

Note: w is a path function.

Heat Transfer: q
(Constant Volume and Pressure)
Constant Volume:

Constant Pressure:
Enthalpy
Enthalpy is the heat given off or absorbed by the
system in a process at a constant pressure.

ΔH = Hproducts – Hreactants
Note:
positive ΔH = endothermic process
negative ΔH = exothermic process
Thermochemical Equations
A chemical reaction equation where enthalpy change is
indicated as well as mass relationship.

In every 1 mole of CH4 gas reacts with 2 moles of O2

gas it produces 1 mole of CO2 gas and 2 moles of H2O
liquid, releasing 890.4 kJ of heat to the surrounding.
 Stoichiometry
Conversion Factors:
1. molar mass – moles to grams
2. mole to mole ratio – changing from one compound
to the other
3. Avogadro’s number – atoms, molecules, particles,
formula units
Practice!
What mass of hydrogen peroxide must decompose to
produce 48.64 g of water?
2 H2O  O2 + H2O
Given: 48.64 g H2O Find: grams of H2O
g H2O  mol H2O  mol H2O2  g H2O2
1. molar mass of H2O
2. mol:mol (H2O:H2O2)
3. molar mass of H2O2
Solution

2 H2O2  O2 + 2H2O
48.64 g H2O 1 mol H2O 2 mol H2O2 34.02 g H2O2
18.02 g H2O 2 mol H2O 1 mol H2O2

= 91.83 g H2O2
Watch this:

https://www.youtube.com/watch?v=lcnIiC8JZg0
Guidelines in Writing Thermochemical
Equations
Practice!
How much heat is evolved when 266 g of white
phosphorus (P4) burn in the air?

P4 (s) + 5O2 (g)  P4O10 (s) ΔH = -3013 kJ

1 𝑚𝑜𝑙 𝑃4 −3013 𝑘𝐽
266 𝑔 𝑃4 𝑥 𝑥 = −6470 𝑘𝐽
123.9 𝑔 𝑃4 1 𝑚𝑜𝑙 𝑃4
Practice!
Use the following enthalpies of reaction to determine
the enthalpy for the reaction of ethylene with fluorine.
C2H4 (g ) + 6F2 (g)  2CF4 (g) + 4HF (g) Δ H = ?

Given:
H2 (g) + F2 (g)  2HF (g) Δ H = -537 kJ
C (s) + 2F2 (g)  CF4 (g) Δ H = -680 kJ
2C (s) + 2H2 (g)  C2H4 (g) Δ H = 52.3 kJ
Solution
C2H4 (g ) + 6F2 (g)  2CF4 (g) + 4HF (g) ΔH=?

[H2 (g) + F2 (g)  2HF (g) Δ H = -537 kJ] multiply by 2

2H2 (g) + 2F2 (g)  4HF (g) Δ H = -1074 kJ

[C (s) + 2F2 (g)  CF4 (g) Δ H = -680 kJ] multiply by 2

2C (s) + 4F2 (g)  2CF4 (g) Δ H = -1360 kJ

[2C (s) + 2H2 (g)  C2H4 (g) Δ H = 52.3 kJ] reverse

C2H4 (g)  2C (s) + 2H2 (g) Δ H = -52.3 kJ
Solution

2H2 (g) + 2F2 (g)  4HF (g) Δ H = -1074 kJ

+ 2C (s) + 4F2 (g)  2CF4 (g) Δ H = -1360 kJ
C2H4 (g)  2C (s) + 2H2 (g) Δ H = -52.3 kJ

C2H4 (g ) + 6F2 (g)  2CF4 (g) + 4HF (g) Δ H = -2486.3 kJ

III. Calorimetry
Calorimetry
Calorimetry is the measurement of heat changes.

Specific heat capacity (cp) – the amount of heat (q)

needed required to raise the temperature of one gram
of a substance by one degree Celsius.
Heat capacity (c) – the amount of heat (q) required
raise the temperature of a given quantity (m) of the
substance by one degree Celsius.
Heat Capacity vs Specific Heat Capacity

higher mass (m) lower mass (m)

same specific heat capacity (cp) same specific heat capacity (cp)
higher heat capacity (c) lower heat capacity (c)

c = m x cp
q = m x cp x ΔT = c x ΔT
Practice!
How much heat is given off when an 869 g iron bar
cools from 94°C to 5°C? (cp = 0.450 J/g • °C)

𝐽
𝑞 = 𝑚𝑐𝑝 ∆𝑇 = 869 𝑔 𝑥 0.450 𝑥 5℃ − 94℃
𝑔 ∙ °𝐶
𝑞 = −34803.45 𝐽
Calorimetry (Constant Volume)
A bomb calorimeter is
used to measure the
change in internal
energy, ΔU, of a
reaction. At constant
volume, this is equal
to qV, the heat of
reaction.
Calorimetry (Constant Pressure)

A constant- pressure calorimeter

measures the change in enthalpy
(ΔH) of a reaction occurring in
solution, during which the
pressure remains constant.
Under these conditions, the
change in enthalpy of the
reaction is equal to the
measured heat.
Calorimetry Calculations
qrxn = -qex
qex = mwater cp(water) ΔT + ccal ΔT

Bomb Calorimeter
ΔE = qv

Coffee-cup Calorimeter
ΔH = qp
Practice!
A student heats a 5.0 g sample of an unknown metal to
a temperature of 207 °C, and then drops the sample into
a coffee-cup calorimeter containing 36.0 g of water at
25.0 °C. After thermal equilibrium has been established,
the final temperature of the water in the calorimeter is
26.0 °C. What is the specific heat of the unknown metal?
(The specific heat of water is 4.18 J/g·°C). Assume that
the coffee-cup calorimeter is adiabatic.
Solution:
qrxn = -qex

qmetal = -qwater

Mmetalcp(metal)ΔTmetal = -mwatercp(water)ΔTwater

(5.0 g) cpmetal(26.0 °C - 207 °C) = -(36.0 g)(4.18 J/𝑔∙°𝐶)(26.0 °C - 25 °C)

cp(metal) = 0.166 J/𝑔∙°𝐶

 A Curious Case

Heat of combustions are usually measured in a bomb

calorimeter. Why are the values presented in literatures
are in terms of enthalpy if we know that enthalpy is a bit
complicated to be derived in a bomb calorimeter?

Answer: The confusion in terms lies in their context in

the statements!
Sample Problem
A 1.000 g sample octane (C8H18) is burned in a bomb
calorimeter containing 1200 grams of water at an initial
temperature of 25.00°C. After the reaction, the final
temperature of the water is 33.20°C. The heat capacity
of the calorimeter (also known as the calorimeter
constant) is 837 J/g°C. The specific heat of water is
4.184 J/g°C. Calculate the heat of combustion of octane
in kJ/mol.
Solution
qrxn = -qex

qrxn = -(qwater + qCal)

qwater = mwatercp(water)ΔTwater
= (1200 g)(4.18 J/𝑔∙°𝐶)(33.20°C - 25 °C) = 41.2 kJ

qcal = ccal ΔT = (837J/°𝐶)(33.20°C - 25 °C) = 6.86 kJ

qrxn = -(41.2 kJ + 6.86kJ) = -48.1 kJ

Note: 1 g of octane produces -48.1 kJ and 1 mol octane weighs 114 grams
ΔHc = (-48.1 kJ/g)(114 g/mol) = -5483 kJ/mol
More Enthalpy Problems
- Standard Enthalpy of Formation and Reaction
- Hess’ Law
- Heat of Solution and Dilution
Standard Enthalpy of Formation and
Reaction
Standard enthalpy of formation (ΔHf0) is the heat
change that results when one mole of a compound is
formed from its elements at a pressure of 1
atm.
- ΔHf0 of any element in its most stable form = zero.
- There is no way to measure the absolute value of the
enthalpy of a substance, only the approximate values
to an arbitrary reference can be determined.
Standard Enthalpy of Formation and
Reaction
The standard enthalpy of reaction (ΔHrxn0) is the
enthalpy of a reaction carried out at 1 atm.

aA + bB  cC + dD

ΔHrxn0 = [cΔHf0(C) + dΔHf0(D)] - [aΔHf0(A) + bΔHf0(B)]

ΔHrxn0 = ΣnΔHf0(products) - ΣnΔHf0(reactants)
Practice!
Benzene (C6H6) burns in air to produce carbon dioxide
and liquid water. How much heat is released per mole of
benzene combusted? The ΔHf0 of benzene is 49.04
kJ/mol, ΔHf0 of CO2 is –393.5 kJ/mol and –187.6
kJ/mol for ΔHf0 of H2O.

2C6H6(l) + 15 O2(g)  12 CO2(g) + 6 H2O(l)

Solution:
2C6H6(l) + 15 O2(g)  12 CO2(g) + 6 H2O(l)

ΔHrxn0 = ΣnΔHf0(products) - ΣnΔHf0(reactants)

ΔHrxn0 = [12ΔHf0(CO2) + 6ΔHf0(H2O)] - [2ΔHf0(C6H6) + 15ΔHf0(O2)]

ΔHrxn0 = [12(-393.5)+ 6(-187.6)] - [2(49.04)+ 15(0)]

ΔHrxn0 = -5945.68 kJ

-5945.68 kJ/2 mol benzene = -2973 kJ/mol

Hess’ Law

Hess' Law of Constant Heat Summation (or just Hess'

Law) states that regardless of the multiple stages or
steps of a reaction, the total enthalpy change for the
reaction is the sum of all changes. This law is a
manifestation that enthalpy is a state function.
Hess’ Law
Practice!
Calculate the standard enthalpy of formation of CS2(l)
given that:

Cgraphite + O2(g)  CO2(g) ΔHrxn0 = -393.5 kJ

Srhombic + O2(g)  SO2(g) ΔHrxn0 = -296.1 kJ
CS2(l) + 3 O2(g)  CO2(g) + 2SO2(g) ΔHrxn0 = -1072 kJ
Solution:
1. You need to write the balanced enthalpy of formation
equation for CS2. CS2 is formed between the reaction of
C and S:

Cgraphite + 2Srhombic  CS2(l)

Solution:
2. a. Use the given reactions to get the desired reaction
for the formation of CS2. The C (graphite) is found in the
reactant sides as well as the S (rhombic), so
you will keep the equation as it is.

Cgraphite + O2(g)  CO2(g) ΔHrxn0 = -393.5 kJ

Srhombic + O2(g)  SO2(g) ΔHrxn0 = -296.1 kJ
Solution:
2. b. Notice that the desired reaction uses 2 moles of S
(rhombic) so we need to multiply the given equation for
S (rhombic) by 2:

Cgraphite + O2(g)  CO2(g) ΔHrxn0 = -393.5 kJ

2Srhombic + 2O2(g)  2SO2(g) ΔHrxn0 = 2 x -296.1kJ
Solution:
2.c. Now the desired product is in the reactant side of
the given equation, so we need to reverse the given
reaction for CS2 and change the sign of ΔHrxn0 :

CO2(g) + 2SO2(g)  CS2(l) + 3 O2(g) ΔHrxn0 = 1072 kJ

Solution:
3. After rearranging the given reactions to have each
species to be at the same side and the same number of
moles with the desired reaction, you can now combine
them and cancel all the same species in each reaction.

4. Add all the ΔHrxn0 of all the rearranged given reactions

to get the ΔHrxn0 of the desired reaction.
Solution:

Cgraphite + O2(g)  CO2(g) ΔHrxn0 = - 393.5 kJ

+ 2Srhombic + 2O2(g)  2SO2(g) ΔHrxn0 = -592.2 kJ
CO2(g) + 2SO2(g)  CS2(l) + 3 O2(g) ΔHrxn0 = 1072 kJ

Cgraphite + 2Srhombic  CS2(l) ΔHrxn0 = 86.3 kJ

Heat of Solution and Dilution

The heat of solution or enthalpy of solution (ΔHsol)

refers to the heat produced or absorbed when a given
amount of solute is dissolved in a given amount of
solvent.

NH4NO3(s)  NH+(aq) + NO3-(aq) ΔHsol = 25.7 kJ

Practice!
The molar heat of solution, ΔHsol, of NaOH is -445.1
kJ/mol. In a certain experiment, 5.00 g of NaOH is
completely dissolved in 1.000 L of 20.0°C water in a
foam cup calorimeter. Assuming no heat loss, calculate
the final temperature of the water.
Solution:
1 𝑚𝑜𝑙 𝑁𝑎𝑂𝐻 −445.1 𝑘𝐽 1000 𝐽
𝑞 = 5.00 𝑔 𝑁𝑎𝑂𝐻 𝑥 𝑥 𝑥
40.0 𝑔 𝑁𝑎𝑂𝐻 1 𝑚𝑜𝑙 𝑁𝑎𝑂𝐻 1 𝑘𝐽
= −5.56 𝑥 104 𝐽

𝑞 = 𝑚𝑐𝑝 ∆𝑇
𝑞 −5.56 𝑥 104 𝐽
∆𝑇 = = = 13.2°𝐶
𝑚𝑐𝑝 1005 𝑔 𝑥 4.18 𝐽
𝑔 ∙ °𝐶

𝑻𝒇𝒊𝒏𝒂𝒍 = 𝟐𝟎°𝑪 + 𝟏𝟑. 𝟐° = 𝟑𝟑. 𝟐°𝑪