[

CHM031L CHEMISTRY FOR

ENGINEERS (Laboratory)

THERMODYNAMICS
[LEARNING OBJECTIVES
§ Recall basic concepts and terminologies in
thermodynamics such as
üHeat and Temperature
üHeat capacity, molar heat capacity, specific heat
capacity
üOpen system, closed system, isolated system,
üEndothermic and exothermic,
üSpontaneity of Reactions
üInternal energy, enthalpy, entropy,
üCalorimetry
üHess’s Law
[THERMODYNAMICS
Study of energy and
its inter-conversion
[ENERGY
q Capacity to do work
[ENERGY
q Capacity to do work
[FORMS OF ENERGY
q Radiant Energy
- comes from the sun and
is earth’s primary
energy source
[FORMS OF ENERGY

H2O
CO2

O2
C6H12O6
[FORMS OF ENERGY
q Chemical Energy
- Energy stored within the bonds of chemical
substances
H2O
CO2

O2
C6H12O6
[FORMS OF ENERGY
q Chemical Energy
- Energy stored within the bonds of chemical
substances
H2O
CO2

O2
C6H12O6
[FORMS OF ENERGY
q Thermal Energy
- Energy associated with the random motion of
atoms and molecules
[FORMS OF ENERGY
q Potential Energy
- Energy available
by virtue of an
object’s position
[FORMS OF ENERGY
q Nuclear Energy
- Energy stored within the collection of
neutrons and protons in the atom
[FORMS OF ENERGY
[
LAW OF CONSERVATION OF ENERGY
[
LAW OF CONSERVATION OF ENERGY
[ENERGY UNITS
q Heat energy is often measured in calories, cal, or
Joules, J, (kg-m2/s2)

q CALORIE – energy required to heat 1.00 g pure

liquid water by 1.00 degree Celsius
[HEAT
Heat, q, is the transfer of thermal energy between two
bodies that are at different temperatures.

Temperature is a measure of the thermal energy.

[HEAT
Heat, q, is the transfer of thermal energy between two
bodies that are at different temperatures.

UNIVERSE
System
= object of study
Surrounding
= region outside the system
Boundary
= separating interface
OPEN SYSTEM
CLOSED SYSTEM
ISOLATED SYSTEM
OPEN SYSTEM
CLOSED SYSTEM
ISOLATED SYSTEM
OPEN CLOSED ISOLATED

THREE TYPES OF SYSTEMS

[ Work
q WORK, W
- Done when an object is moved against an opposing force
- Doing work is equivalent to raising a weight somewhere
in the surrounding (opposing the gravity)

Movable piston
GAS Expansion of gas
- Piston is pushed upwards
- Gas does work
 Work Done by the System
w = F x d
DV > 0
w = -PoppDV
-PoppDV < 0
F wsys < 0
P x V = x d3 = F x d = w
d2

initial final
 [ INTERNAL ENERGY
INTERNAL ENERGY, U
§ total energy of a system
§ Total kinetic energy (KE) and potential energy (PE) of the
particles in the system
CONTRIBUTIONS TO U OF A SUBSTANCE
§ KE of the motion of individual particles
§ PE that arises from interactions between particles
§ KE and PE of nuclei and electrons within the
individual particles
Absolute value of U cannot be measured
Only ΔU can be measured
[THERMODYNAMICS
- Involves the study of the changes in the state of the
system

Defined by values of all

relevant macroscopic
properties . Examples:
pressure, volume,
temperature
State functions are properties that are determined by the
state of the system, regardless of how that condition was
achieved.

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.
[ FIRST LAW OF THERMODYNAMICS
“ The internal energy of an isolated system is constant”

Conservation of Energy: The energy of the universe is constant.

DUsystem + DUsurroundings = 0
Closed system
DUsystem = -DUsurroundings Change in U (∆U) is equal
to the E that passes
through a boundary as
Isolated system heat (q) or work (W)
constant U (∆U =0)
q = 0; W = 0
∆U = q + W
[
FIRST LAW OF THERMODYNAMICS
∆U = q + W
∆U (+) INCREASE in internal E of system
∆U (-) DECREASE in internal E of system
q (+) heat ABSORBED by the system from
surrounding (ENDOTHERMIC)
q (-) heat RELEASED by the system from
surrounding (EXOTHERMIC)
W (+) work done ON the system by the
surrounding
W (-) work done BY the system on the
surrounding
[
FIRST LAW OF THERMODYNAMICS
∆U = q + W

∆U = q ∆U = W
No work done No heat transferred
 Work IN

Heat IN Heat OUT

Work OUT
∆𝑈 = +515𝐽 + −218𝐽 = 297𝐽
Q = (+) because heat is added
W = (-) because the gas (system) does the work
Sample problem 1

• Consider the power stroke. Suppose the gas

volume expands from 0.05 L to 0.4 L against
1 atm pressure while releasing 100 J of
heat. Calculate the change in internal
energy of the system.
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
(b)against a constant pressure of 1.2 atm
A simple sketch of the situation is helpful here:

• The work done in gas expansion is equal to the

product of the external, opposing pressure and the
change in volume.
• What is the conversion factor between L · atm and J?

101.3 𝐽 = 1 𝐿 2 𝑎𝑡𝑚
[Calorimetry
is the measurement of state variables for the purpose
of deriving the heat transfer associated with changes
of its state due for example to :

• Chemical reactions
• Physical changes/
Phase transitions
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.

The molar heat capacity (Cm) of a substance is the amount

of heat (q) required to raise the temperature of one mole
of the substance by one degree Celsius.

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.
C = m x s
Heat (q) absorbed or released:
q = m x s x DT q = C x DT DT = Tfinal - Tinitial
[
Calorimetry
[Sample Problem
A 466-g sample of water is heated from 8.50°C to
74.60°C. Calculate the amount of heat absorbed (q) (in
kilojoules) by the water. Specific heat of water is 4.184
J/g∙°C
[Sample Problem
A 466-g sample of water is heated from 8.50°C to
74.60°C. Calculate the amount of heat absorbed (q) (in
kilojoules) by the water. Specific heat of water is 4.184
J/g∙°C

𝑞 = 𝑚 𝑥 𝑠 𝑥 ∆𝑇
𝑞 = 466 𝑔 4.184𝐽/𝑔 2> 𝐶 74.60> 𝐶 − 8.50> 𝐶
𝑞 = 128878 𝐽 ≈ 129 𝑘𝐽
Learning Check
A 26.2 g piece of copper metal is heated from
21.5°C to 201.6°C. Calculate the amount of
heat absorbed by the metal. The specific heat
of Cu is 0.385 J/g·°C

Answer: 1816.67 J
Learning Check
The heat capacity of 5 grams of gold is
0.645 J/°C.
a) What is the specific heat of gold?
b) What is the molar heat capacity of
gold? Molar mass of gold is 196.97
g/mol

Answers:
a. 0.129 J/goC
b. 25.4 J/moloC
Learning Check

A beaker contains 125.0 g of ethanol at

25.30°C. If the ethanol absorbs 1125 J of
heat without losing heat to the
surroundings, what will be the final
temperature of the ethanol? The specific
heat of ethanol is 2.460 J/g°C

Answer: 28.96oC
51
SEATWORK (1/4 yellow sheet)
1. Aluminum metal has a specific heat of 0.900
J/g·°C. Calculate the amount of heat required
to raise the temperature of 10.5 moles of Al
from 30.5 °C to 225°C
2. A piece of copper with a mass of 218 g has a
heat capacity of 83.9 J/°C. What is the
specific heat of copper?
HOMEWORK (1/4 yellow sheet)
1. Three separate 3.5g blocks of Al, Cu, and Fe
at the same temperature each absorb same
amount of heat. Which block reaches the
highest temperature? The specific heats of
Al, Cu and Fe are 0.900 J/g·°C, 0.385 J/g·°C,
and 0.444 J/g·°C, respectively.
2. A 12 moles sample of H2O at 85°C is cooled.
The water loses a total of 15 kJ of energy in
the cooling process. What is the final
temperature of the water? The specific heat
of water is 4.184 J/g·°C
[LEARNING OBJECTIVES
q Describe how changes in enthalpy and
thermal energy accompanying a chemical
reaction can be measured calorimetrically.
q Solve problems involving determination of
specific heat, heat capacity, heat loss or heat
gained by system and enthalpy of reaction
using calorimetry.
q Interpret thermochemical equations for
combustion and formation reactions.
[LEARNING OBJECTIVES
q Use thermochemical equations and
stoichiometry to determine amount of heat
lost or gained in a chemical reaction
q Calculate the molar enthalpy of dissolution
from calorimeter experimental data.
[USEFUL EQUATIONS
q = m x s x DT C = m x s
q = C x DT C = Cm x mol
DT = Tfinal - Tinitial Cm = MM x s
 Constant-Volume Calorimetry

qsys + qsurr = 0

qsys = qrxn
qsurr = qwater + qbomb
qrxn + qwater + qbomb = 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!
Sample Problem
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
Note: qwater + qbomb is
heat of reaction of naphthalene.
combined because
the heat capacity
qrxn + qwater + qbomb = 0 given is for the
qrxn = - (qwater + qbomb) = - qcal combined bomb and
water.
Solution The heat absorbed by the bomb and water is equal to
the product of the heat capacity and the temperature change.

Assuming no heat is lost to the surroundings, we write

qsys = qrxn = - qcal

The heat change of the reaction is − 57.66 kJ.

 Constant-Pressure Calorimetry

qsys + qsurr = 0

qsys = qrxn
qsurr = qwater + qcal
qrxn + qwater + qcal = 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!

Sample Problem
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 22.50°C to 23.17°C.

What is the specific heat of

the lead pellet?
Strategy A sketch of the initial and final situation is as follows:

ü masses of water and the lead pellet

ü initial and final temperatures
ü Assuming no heat is lost to the surroundings, we can equate
the heat lost by the lead pellet to the heat gained by the
water.
ü Knowing the specific heat of water, we can then calculate the
specific heat of lead.
Solution qsys = qPb
qsurr = qwater + qcal
qcal = 0 (negligible heat capacity)

OR

The heat gained by the water is given by

𝑞CDE = 𝑚𝑠∆𝑇
where m and s are the mass and specific heat and

DT = Tfinal − Tinitial
Therefore,

Because the heat lost by the lead pellet is equal to the heat
gained by the water, qPb = −280.3 J. Solving for the specific
heat of Pb, we write

𝑞FG = 𝑚𝑠∆𝑇
65
Sample Problem
A quantity of 100.0 mL of 0.500 M HCl was mixed with 100.0
mL of 0.500 M 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:

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).
 6.8
Strategy
Because the temperature rose, the neutralization reaction is
exothermic.

How do we calculate the heat absorbed by the combined

solution?

What is the heat of the reaction?

What is the conversion factor for expressing the heat of

reaction on a molar basis?
 qsys + qsurr = 0
Solution qsys = qrxn
qsurr = qsoln + qcal (qcal = 0 – negligible heat capacity)
qrxn = −qsoln
where qsoln is the heat absorbed by the combined solution.

Because the density of the solution is 1.00 g/mL, the mass of a

100-mL solution is 100 g. Thus,
𝑞H>IJ = 𝑚𝑠∆𝑇

Because qrxn = −qsoln, qrxn = −2.81 kJ.

From the molarities given, the number of moles of both HCl and
NaOH in 1.00 × 102 mL solution is

Therefore, the heat of neutralization when 1.00 mole of HCl

reacts with 1.00 mole of NaOH is
Chemistry in Action: Making Snow

DU = q + w

q = 0

w < 0, DU < 0

DU = CDT

DT < 0, SNOW!
Enthalpy and the First Law of Thermodynamics
DU = q + w
At constant pressure:
q = DH and w = -PDV
DU = DH - PDV Relationship of
DH = DU + PDV DH and DU

71
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)

Schematic of Exothermic and Endothermic Processes

73
Enthalpy (H) is used to quantify the heat 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

Hproducts < Hreactants Hproducts > Hreactants

DH < 0 DH > 0
 Thermochemical Equations

Is DH negative or positive?

System absorbs heat

Endothermic

DH > 0

6.01 kJ are absorbed for every 1 mole of ice that

melts at 00C and 1 atm.

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

 Thermochemical Equations

Is DH negative or positive?

System gives off heat

Exothermic

DH < 0

890.4 kJ are released for every 1 mole of methane

that is combusted at 250C and 1 atm.

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

Given the thermochemical equation

2SO2(g) + O2 (g) à 2SO3 (g) ΔH = -198.2 kJ

Calculate the heat evolved when 87.9 g of SO2 (molar mass

=64.07 g/mol) is converted to SO3
Solution We need to first calculate the number of moles of
SO2 in 87.9 g of the compound and then find the number of
kilojoules produced from the exothermic reaction. The
sequence of conversions is as follows:

Therefore, the enthalpy change for this reaction is given by

and the heat released to the surroundings is 136 kJ.

Check
Because 87.9 g is less than twice the molar mass of SO2
(2 × 64.07 g) as shown in the preceding thermochemical
equation, we expect the heat released to be smaller than
198.2 kJ.
 A Comparison of DH and DU
2Na(s) + 2H2O(l) 2NaOH(aq) + H2(g) DH = -367.5 kJ/mol

DU = DH - PDV At 25 oC, 1 mole H2 = 24.5 L at 1 atm

PDV = 1 atm x 24.5 L = 2.5 kJ

DU = -367.5 kJ/mol – 2.5 kJ/mol = -370.0 kJ/mol

82
 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:

Carbon monoxide burns in

air to form carbon dioxide.
 6.4
Strategy
We are given the enthalpy change, DH, for the reaction and are
asked to calculate the change in internal energy, DU.

Therefore, we need Equation (6.10).

What is the change in the number of moles of gases?

D H is given in kilojoules, so what units should we use for R?

 6.4
Solution From the chemical equation we see that 3 moles of
gases are converted to 2 moles of gases so that

Using 8.314 J/K · mol for R and T = 298 K in Equation (6.10),

we write
Standard enthalpy of formation

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.

DH0f (O2) = 0 DH0f (C, graphite) = 0

DH0f (O3) = 142 kJ/mol DH0f (C, diamond) = 1.90 kJ/mol

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 (DH0) as a reference
point for all enthalpy expressions.
f

Standard enthalpy of formation (DH0) is the heat change that results when one mole
f
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.

DH0 (O2) = 0 DH0 (C, graphite) = 0

f f
DH0 (O3) = 142 kJ/mol DH0 (C, diamond) = 1.90 kJ/mol
f f
87
88
The reaction that represents the standard enthalpy of
formation for benzene (C6H6) is:

A) 6 C(diamond) + 3 H2(g) → C6H6(l)

B) 6 C(graphite) + 6 H(g) → C6H6(l)
C) C6H6(l) + 15/2 O2(g) → 6 CO2(g) + 3 H2O(g)
D) 6 C(graphite) + 3 H2(g) → C6H6(l)

89
Which of the following has a DH°f = 0 kJ/mol?
A) NO(g)
B) CS2(l)
C) Fe2+(aq)
D) H2O(l)
E) N2(g)
Answer: E
N2(g) is the most stable
form for Nitrogen.
90
The standard enthalpy of reaction(DH0rxn) is the enthalpy of a
reaction carried out at 1 atm.

aA + bB cC + dD

DH0rxn= [ cDH0 (C) + dDH0 (D) ] - [ aDH0f (A) + bDHf0 (B) ]

f f

DH0rxn= S nDH0f (products) - S mDH0f (reactants)

n and m are stoichiometric coefficients

91
The thermite reaction involves
aluminum and iron(III) oxide

This reaction is highly exothermic

and the liquid iron formed is used
to weld metals.

Calculate the heat released in

kilojoules.

The molten iron formed in a thermite

reaction is run down into a mold
between the ends of two railroad rails.
On cooling, the rails are welded
together.
Al (s) = 0 kJ/mole
Fe2O3 (s) = - 822.2 kJ/mole

Al2O3 (s) = -1669.9 kJ/mole

Fe (l) = 12.40 kJ/mole

The molten iron formed in a thermite

reaction is run down into a mold
between the ends of two railroad rails.
On cooling, the rails are welded
together.
Strategy
The enthalpy of a reaction is the difference between the sum of
the enthalpies of the products and the sum of the enthalpies of
the reactants.

The enthalpy of each species (reactant or product) is given by

its stoichiometric coefficient times the standard enthalpy of
formation of the species.
Solution
 Sample Problem
Octane (C8H18) undergoes combustion according to the
following thermochemical equation:

2C8H18(l) + 25O2(g) 16CO2(g) + 18H2O(l) ΔH°rxn = –11,020 kJ.

Given that
ΔH°f[CO2(g)] = –393.5 kJ/mol
ΔH°f[H2O(l)] = –285.8 kJ/mol
Calculate the standard enthalpy of formation of octane.
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.)
Remember the rules when
reversing a reaction or
multiplying by a certain factor.
 6.9
Calculate the standard enthalpy of formation of acetylene
(C2H2) from its elements:

The equations for each step and the corresponding enthalpy

changes are
 6.9
Strategy Our goal here is to calculate the enthalpy change for
the formation of C2H2 from its elements C and H2. The reaction
does not occur directly, however, so we must use an indirect
route using the information given by Equations (a), (b), and (c).

Solution Looking at the synthesis of C2H2, we need 2 moles of

graphite as reactant. So we multiply Equation (a) by 2 to get

Next, we need 1 mole of H2 as a reactant and this is provided

by Equation (b). Last, we need 1 mole of C2H2 as a product.
 6.9
Equation (c) has 2 moles of C2H2 as a reactant so we need to
reverse the equation and divide it by 2:

Adding Equations (d), (b), and (e) together, we get

 6.9
Therefore,

This value means that when 1 mole of C2H2 is synthesized from

2 moles of C(graphite) and 1 mole of H2, 226.6 kJ of heat are
absorbed by the reacting system from the surroundings. Thus,
this is an endothermic process.
 SEATWORK

Water gas is the name for the industrially important mixture

of CO and H2 which is prepared by passing steam over a hot
charcoal bed at 1000°C as shown by the reaction

C(s) + H2O (g) à CO(g) + H2(g)

Given the following thermochemical equations, determine the ΔH of the
above reaction
C(s) + O2(g) à CO2(g) ΔH = -393.5 kJ
2CO(g) + O2(g) à 2 CO2(g) ΔH = -566.0 kJ
2H2(g) + O2(g) à 2 H2O(g) ΔH = -483.6 kJ
The enthalpy of solution (DHsoln) is the heat generated or absorbed when a certain amount
of solute dissolves in a certain amount of solvent.

DHsoln = Hsoln - Hcomponents

106
 The Solution Process for NaCl

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

107
[
Spontaneity

Some things happen naturally; some things don’t

SPONTANEOUS NON-SPONTANEOUS

Does NOT require work to

bring it about
 [ Spontaneity

Can be determined using ΔG (Gibbs Free Energy) values

ΔG = ΔH -T ΔS
ΔG = (-) SPONTANEOUS
ΔG = (+) NON-SPONTANEOUS
ΔH = enthalpy change
T = temperature in Kelvin
ΔS = entropy change
[ENTROPY, S

q a state function used to express the 2nd law of

thermodynamics
q measure of energy dispersed in the process or
the molecular disorder of the system (the
amount of molecular randomness in a system)
LMNO
Δ𝑆 =
P

For constant pressure:

ΔH
Δ𝑆 = Tb = boiling point in K
PQ