Principles of General Chemistry, 2nd ed. By M.

Silberberg
Chemistry, 8th ed. by W. Whitten, R. Davis, R., M. L. Peck, and G. Stanley.

Objectives
Chemical Thermodynamics:
Heat and Thermochemistry 1. Define thermodynamics &
thermochemistry
2. Define energy, heat and other
thermodynamic terms
3. Define enthalpy
4. Discuss thermochemical equations
5. Define spontaneity, entropy and Gibb’s
free energy

Thermodynamics &
Why study thermochemistry?
Thermochemistry
• It allows us to predict whether a
Thermodynamics is the study of heat
certain process would occur
and its transformations
spontaneously or not
to and from other forms of energy
• However, its limitations is that, it
Thermochemistry is a branch of can not predict how fast a reaction
thermodynamics that deals with would occur (kinetics)
the heat involved with chemical and
physical changes

Energy and heat Fundamental Laws

ENERGY – the capacity to do work 1st Law of Thermodynamics
• KINETIC ENERGY – due to motion (will be explained in
the gases part) • The combined amount of matter and
• POTENTIAL ENERGY – due to position or composition energy in the universe is constant
(main discussion in thermochemistry)
• Units: joule (J) = 1 N·m = 1 kg·m2/s2 and calorie (cal) =
4.184 joules
Law of Conservation of Energy
HEAT – energy transferred between a • Energy is neither created nor destroyed
system and its surroundings as a result
of temperature difference
Thermodynamic terms Thermodynamic Systems
– defined by the set of conditions that
UNIVERSE = Systems + surroundings specify all of its properties
• number of moles and identity of each substance
• physical states of each substance
SYSTEMS = substances involved in the • temperature of the system (standard state = 298 K)
physical or chemical changes under • pressure of the system (standard state ( 1.00 atm)

investigation types:
1. Open – energy and matter can move in and out
of the system freely
SURROUNDINGS = environment around
2. Closed - matter is confined only in the system
the system

Thermodynamic Systems Thermodynamic Systems

1. Systems tend toward a state of 2. Systems tend toward a state of
minimum potential energy. maximum disorder.

Some examples of this include: Common examples of this are:

• H2O flows downhill. – A mirror shatters when dropped and does
• Objects fall when dropped. not reform.
The energy change for these two examples is: – It is easy to scramble an egg and difficult to
unscramble it.
• Epotential = mgh
– Food dye when dropped into water
• ∆Epotential = mg(∆h) disperses.

Thermodynamic Universe Thermodynamic Universe

• system is composed of particles with their own
internal energies (E), i.e. when a change
occurs, the E of the surrounding also changes
• ∆E = q (heat) + w (work)

∆Euniverse = ∆Esystem + ∆Esurroundings

Thermodynamic Universe Thermodynamic Universe
When gasoline burns in a car engine, the heat released
causes the products CO2 and H2O to expand, which pushes
the pistons outward. Excess heat is removed by the car’s
cooling system. If the expanding gases do 451 J of work on
the pistons and the system loses 325 J to the surroundings
∆E) in J, kJ, and kcal.
as heat, calculate the change in energy (∆

SOLUTION: q = - 325 J w = - 451 J

∆E = q + w = -325 J + (-451 J) = -776 J

kJ
-776 J x = -0.776 kJ
103J

-0.776 kJ x kcal = -0.185 kcal

4.184 kJ

Heat flow Heat flow

• Heat – denoted by the symbol q
q > 0 : (endothermic process)
• heat flows from the surroundings to the
system
q < 0 : (exothermic process)
• heat flows from the system to the
surroundings

Heat flow
Enthalpy Enthalpy of reaction, ∆Hrxn
• denoted as H, a thermodynamic quantity – this quantity will tell us if the reaction
used to describe heat changes taking place produces or consumes heat
at constant pressure
• chemical energy in terms of heat or “heat
content”
• a state property (a.k.a state function)
• depend only on the initial and final state of
the system
∆X =Xfinal – Xinitial

Enthalpy of reaction, ∆Hrxn

• ∆Hrxn > 0 : ENDOTHERMIC REACTION
heat is absorbed by the chemical
reaction

• ∆Hrxn < 0 : EXOTHERMIC REACTION

heat is released by the chemical
reaction

Thermochemical Equations Thermochemical Equations

• chemical equations that show the
enthalpy of reaction
• should be balanced, the phases or
states are indicated and applies to a
specific temperature (usually 25oC
unless specified otherwise)
Thermochemical Equations
Thermochemical Rules
• Example
• H2(g) + Cl2(g) → 2 HCl(g) ∆H = -185 kJ
• 2 H2(g) + 2 Cl2(g) → 4 HCl(g) ∆H = -370 kJ
• ½ H 2(g) + ½ Cl 2(g) → HCl(g) ∆H = -92.5 kJ
Thermochemical Rules
3. The value of ∆H for a reaction is the
same whether it occurs in one step or
in a series of steps (Hess’s law)
• ∆Htotal = ∆Hrxn1 + ∆Hrxn2 + ∆Hrxn3 + …
Thermochemical Rules
1. The magnitude of the heat of reaction
is directly proportional to the amount
of the limiting reactant.
• qrxn = ∆Hrxn·nLR
(depends on limiting reactant)
Thermochemical Rules
2. The ∆H for a reaction is equal in
magnitude but opposite in sign to ∆H
for the reverse reaction.
• H2(g) + Cl2(g) → 2 HCl(g) ∆H = (-) 185 kJ
• 2 HCl(g) → H2(g) + Cl2(g) ∆H = (+) 185 kJ
Thermochemical Rules
4. The physical states of all species are
important and must be specified.
5. The value of ∆H usually does not
change significantly with moderate
changes in temperature.
Thermochemical Stoichiometry Thermochemical Stoichiometry
The major source of aluminum in the world is
relationship between amount (mol) of bauxite (mostly aluminum oxide). Its thermal
substance and the heat (kJ) transferred decomposition can be represented by
during a reaction
Al2O3(s) 2Al(s) + O2(g) ∆Hrxn = 1676 kJ
If aluminum is produced this way, how many grams
of aluminum can form when 1.000 x 103 kJ of heat
is transferred?
SOLUTION:

1.000 x 103 kJ x 2 mol Al x 26.98 g Al = 32.20 g Al

1676 kJ 1 mol Al

Standard Molar Enthalpies Standard Molar Enthalpies

of Formation, ∆Hfo of Formation, ∆Hfo
• the enthalpy for the reaction in which one
• elements in their most stable forms at
mole of a substance is formed from its 298.15 K and 1.000 atm are zero.
constituent elements.
substances ∆Hfo substances ∆Hfo
• example: MgCl2
Ca(s) 0.00 N2(g) 0.00
CaO(s) -635 NH3(g) -45.9
M g (s ) + C l 2 ( g ) → M g C l 2 ( s ) + 6 4 1.8 k J
C(graphite) 0.00 Na(s) 0.00
∆H o
f M g C l 2 (s ) = − 6 4 1.8 k J / m o l C(diamond) 1.90 Na(g) 107

Hess’s Law Hess’s Law

Two gaseous pollutants that form in auto exhaust are CO and
NO. An environmental chemist is studying ways to convert
• Heat Summation - states that the them to less harmful gases through the following equation:
1
enthalpy change for a reaction is the CO(g) + NO(g) CO2(g) + N2(g) ∆H = ?
2
Given the ff., calculate the unknown ∆H:
same whether it occurs by one step
Eq. A: CO(g) + 1 O2(g) CO2(g) ∆HA = -283.0 kJ
or by any (hypothetical) series of 2
Eq. B: N2(g) + O2(g) 2NO(g) ∆HB = 180.6 kJ
steps.
• Hess’s Law is true because ∆H is a CO(g) + 1 O2(g)
2
CO2(g) ∆HA = -283.0 kJ
1 1
state function. NO(g) N2(g) + O (g) ∆HB = -90.3 kJ
2 2 2

CO(g) + NO(g) CO2(g) + 1 N2(g) ∆Hrxn = -373.3 kJ

2
Hess’s Law Hess’s Law
• Example: Given the following equations and • Use a little algebra and Hess’s Law to get the
∆Ho values ∆H o ( kJ ) appropriate ∆Ho values
[1] 2 N 2( g ) + O 2( g ) → 2 N 2 O ( g ) 164.1 ∆H o (kJ)
1 × [ − 1] N 2 O ( g ) → N 2( g ) + 1 O 2( g ) - 82.05
[2] N 2( g ) + O 2( g ) → 2 NO ( g ) 180.5 2 2
3
2 × [ 2] 3
2 N 2( g ) + 3
2 O 2( g ) → 3 NO ( g ) 270.75
[3] N 2( g ) + 2 O 2( g ) → 2 NO 2 ( g ) 66.4 1
2 × [ − 3] NO 2( g ) → 1
2 N 2( g ) + O 2( g ) - 33.2
• calculate ∆Ho for the reaction below. N 2 O ( g ) + NO 2( g ) → 3 NO ( g ) 155.5
N2O (g) + NO2 (g ) → 3 NO (g) ∆ Ho = ?

“Do unto others what you want

others do unto you”
you”
- Confucius

questions?