Thermochemistry:

Energy Flow and Chemical Change

Thermochemistry: Energy Flow and Chemical Change

Forms of Energy and Their Interconversion
Enthalpy: Heats of Reaction and Chemical Change
Calorimetry: Laboratory Measurement of Heats of Reaction
Stoichiometry of Thermochemical Equations
Hesss Law of Heat Summation
Standard Heats of Reaction (H0rxn)

Thermodynamics is the study of heat and its transformations.

Thermochemistry is a branch of thermodynamics that deals with
the heat involved with chemical and physical changes.
Fundamental premise
When energy is transferred from one object to another,
it appears as work and/or as heat.
For our work we must define a system to study; everything else
then becomes the surroundings.

A chemical system and its surroundings.

the surroundings

the system

Energy diagrams for the transfer of internal energy (E)

between a system and its surroundings.

E = Efinal - Einitial = Eproducts - Ereactants

Heat and work: two forms of energy transfer

Heat (thermal energy, q) energy transferred between a system

and its surroundings as a result of a difference in their
temperatures only.
Work (w) energy transferred when an object is moved by a force.
E = q + w
Numerical values of q and w can be positive and negative
Energy coming in to the system is +.
Energy going out from the system is -.

A system transferring energy as heat only.

A system losing energy as work only.

Zn(s) + 2H+(aq) + 2Cl-(aq)

Energy, E
E<0

work done on
surroundings

H2(g) + Zn2+(aq) + 2Cl-(aq)

The Sign Conventions* for q, w, and E

depends on sizes of q and w

depends on sizes of q and w

* For q: + means system gains heat; - means system loses heat.

* For w: + means word done on system; - means work done by system.

First law of thermodynamics

(law of conservation of energy)

Euniverse = Esystem + Esurroundings = 0

Units of Energy
Joule (J)

1 J = 1 kg*m2/s2

Calorie (cal)

1 cal = 4.18J

British Thermal Unit

1 Btu = 1055 J

Determining the Change in Internal Energy of a System

PROBLEM:

In a reaction, gaseous reactants form a liquid product. The heat

absorbed by the surroundings is 26.0 kcal, and the work done
on the system is 15 Btu. Calculate E (in kJ).

Two different paths for the energy change of a system.

E is a state function property dependant on the current state of the system,

not on the path the system took to reach that state
q and w are not state functions values do depend on the path the system
takes in undergoing the energy change

Pressure-volume
work.

The Meaning of Enthalpy (H)

w = - PV
H = E + PV

H E in
1. Reactions that do not involve gases.

where H is enthalpy

H = E + PV

qp = E + PV = H

2. Reactions in which the number of

moles of gas does not change.
3. Reactions in which the number of
moles of gas does change but q is >>>
PV.

Enthalpy diagrams for exothermic and endothermic processes.

H = Hfinal Hinitial = Hproducts - Hreactants

CH4(g) + 2O2(g)

CO2(g) + 2H2O(g)

H2O(l)

CH4 + 2O2

H2O(g)

H < 0

heat out

Enthalpy, H

Enthalpy, H

Hinitial

H > 0

CO2 + 2H2O

H2O(l)

Hfinal

Exothermic process

H2O(g)

Hfinal

heat in

Hinitial

Endothermic process

Drawing Enthalpy Diagrams and Determining the Sign of H

PROBLEM:

In each of the following cases, determine the sign of H, state

whether the reaction is exothermic or endothermic, and draw
and enthalpy diagram.
(a) H2(g) + 1/2O2(g)

H2O(l) + 285.8kJ

(b) 40.7kJ + H2O(l)

H2O(g)

Specific Heat Capacities of Some Elements, Compounds, and Materials

Substance

Specific Heat
Capacity (J/g*K)

Substance

Specific Heat
Capacity (J/g*K)

Materials

Elements
aluminum, Al

0.900

wood

1.76

graphite,C

0.711

cement

0.88

iron, Fe

0.450

glass

0.84

copper, Cu

0.387

granite

0.79

gold, Au

0.129

steel

0.45

Compounds
water, H2O(l)

4.184

ethyl alcohol, C2H5OH(l)

2.46

ethylene glycol, (CH2OH)2(l)

2.42

carbon tetrachloride, CCl4(l)

0.864

Finding the Quantity of Heat from Specific Heat Capacity

PROBLEM: A layer of copper welded to the bottom of a skillet weighs 125 g.

How much heat is needed to raise the temperature of the
copper layer from 250C to 300.0C? The specific heat capacity
(c) of Cu is 0.387 J/g*K.

Use q = (m)(c)(T)

Finding the Quantity of Heat from Specific Heat Capacity

PROBLEM: Find the heat transferred in kJ when 5.50 L of ethylene glycol

(density = 1.11 g/mL, c = 2.42 J/g*K) in a car radiator cools from
37.0 oC to 25.0 oC.

Coffee-cup calorimeter.

Sample Problem 6.4

Determining the Heat of a Reaction

PROBLEM: A 10.25 carat (1 carat = 0.2000 g) diamond is heated to 74.21 oC and

immersed in 26.05 g of water in a constant pressure calorimeter. The
initial temperature of the water is 27.20 oC. Calculate the T of the
water and of the diamond (cdiamond = 0.519 J/g*K, cwater = 4.184 J/g*K).

AMOUNT (mol)
of compound A

Summary of the relationship between

amount (mol) of substance and the heat
(kJ) transferred during a reaction.

AMOUNT (mol)
of compound B
molar ratio from
balanced equation

HEAT (kJ)
Hrxn (kJ/mol)

gained or lost

Using the Heat of Reaction (Hrxn) to Find Amounts

PROBLEM:

The major source of aluminum in the world is bauxite (mostly

aluminum oxide). Its thermal decomposition can be represented by
Al2O3(s)

2Al(s) + 3/2O2(g)

Hrxn = 1676 kJ

If aluminum is produced this way, how many grams of aluminum can

form when 1.000x103 kJ of heat is transferred?

Using the Heat of Reaction (Hrxn) to Find Amounts

PROBLEM:

Using the following equation, if 137 kJ is given off per mole of C2H4
reacting, how much heat is released when 15.0 kg of C2H6 forms?

C2H4 + H2 C2H6

Using Hesss Law to Calculate an Unknown H

PROBLEM:

Two gaseous pollutants that form in auto exhaust are CO and

NO. An environmental chemist is studying ways to convert
them to less harmful gases through the following equation:
CO(g) + NO(g)

CO2(g) + 1/2N2(g)

H = ?

Given the following information, calculate the unknown H:

Equation A: CO(g) + 1/2O2(g)
Equation B: N2(g) + O2(g)

CO2(g) HA = -283.0 kJ
2NO(g) HB = 180.6 kJ

Selected Standard Heats of Formation at 250C(298K)

Gas = 1 atm
Aqueous solution = 1 M
Pure substance = most stable form at 1 atm and 298 K
Formula
calcium
Ca(s)
CaO(s)
CaCO3(s)

H0f(kJ/mol)
0
-635.1
-1206.9

carbon
C(graphite)
C(diamond)
CO(g)
CO2(g)
CH4(g)
CH3OH(l)
HCN(g)
CSs(l)

0
1.9
-110.5
-393.5
-74.9
-238.6
135
87.9

Formula H0f(kJ/mol)

Formula H0f(kJ/mol)

0
-92.3

hydrogen
H(g)
H2(g)

silver
Ag(s)
AgCl(s)

218
0

sodium

nitrogen
N2(g)
NH3(g)
NO(g)

0
-45.9
90.3

oxygen
O2(g)
O3(g)
H2O(g)

0
143
-241.8

H2O(l)

-285.8

Cl2(g)
HCl(g)

Na(s)
Na(g)
NaCl(s)

0
-127.0

0
107.8
-411.1

sulfur
S8(rhombic) 0
S8(monoclinic) 2
-296.8
SO2(g)
SO3(g)

-396.0

Writing Formation Equations

PROBLEM:

Write balanced equations for the formation of 1 mol of the following

compounds from their elements in their standard states and include
H0f.
(a) Silver chloride, AgCl, a solid at standard conditions.
(b) Calcium carbonate, CaCO3, a solid at standard conditions.
(c) Hydrogen cyanide, HCN, a gas at standard conditions.

Elements

-H0f

formation

Reactants

decomposition

Enthalpy, H

The general process for determining H0rxn from H0f values.

H0f
Hinitial
H0rxn

Products
H0rxn = mH0f(products) - nH0f(reactants)

Hfinal

Calculating the Heat of Reaction from Heats of Formation

PROBLEM: Nitric acid, whose worldwide annual production is about 8 billion
kilograms, is used to make many products, including fertilizer, dyes,
and explosives. The first step in the industrial production process is
the oxidation of ammonia:
4NH3(g) + 5O2(g)

4NO(g) + 6H2O(g)

Calculate H0rxn from H0f values.

H0f NH3 (g) = -45.9 kJ/mol
H0f O2 (g) = 0 kJ/mol
H0f NO (g) = 90.3 kJ/mol
H0f H2O (g) = -241.8 kJ/mol