Chapter 5:

Thermochemistry
Thermochemistry:
Energy
Kinetic & Potential
First Law of Thermo
internal energy, heat & work
endothermic & exothermic processes
state functions
Enthalpy
Enthalpies of Reaction
Calorimetry
heat capacity and specific heat
constant-pressure calorimetry
bomb calorimetry (constant-volume calorimetry)
Hesss Law
Enthalpies of Formation
for calculation of enthalpies of reaction
Foods and Fuels
Energy
work is a form of energy w = F x d
energy is the capacity to do work or transfer heat
Kinetic Energy
energy of motion E = mv
2

potential energy
energy of position
applies to electrostatic energy
applies to chemical energy (energy of bonds)
energy units
one joule = energy of a 2 kg mass moving at 1
m/s
E = mv
2
()(2 kg) (m/s)
2
= kg m
2
/s
2
= 1 J
1 cal = 4.184 J 1 kcal = 1 food calorie (Cal)

Systems & Surroundings
system -- chemicals in the reaction



surroundings -- container & all outside environment
closed system can exchange energy (but not matter)
with its surroundings
2H
2(g)
+ O
2(g)


2H
2
O
(l)
+ energy
(system)
energy
(as heat
or work)
no exchg
of matter
with
surroundings
Closed System
First Law of Thermo.
Energy is always conserved
any energy lost by system, must be gained by
surroundings
Internal Energy -- total energy of system
combination of all potential and kinetic energy of
system
incl. motions & interactions of of all components
we measure the changes in energy
E = E
final
- E
initial

+ E = E
final
> E
initial
system has gained E from
surroundings
- E = E
final
< E
initial
system has lost E to
surroundings
Relating E to heat and work
E = q + w q is positive if heat goes from
surroundings to system

w is positive if work is done on
system by surroundings


system
surroundings
+q +w
system
surroundings
- q - w
Endothermic
system absorbs heat or heat flows into the
system
Exothermic
system gives off heat or heat flows out of the
system
State Function
a property of a system that is determined by
specifying its condition or state (T, P, etc.)
internal energy is a state function, \ E depends
only on E
final
& E
initial

Enthalpy
for most reactions, most of the energy exchanged
is in the form of heat, that heat transfer is called
enthalpy, H
enthalpy is a state function
like internal energy, we can only measure the
change in enthalpy, H
H = q
p
when the process occurs under constant
pressure
H = H
final
- H
initial
= q
p

- H exothermic process
+H endothermic process
system
surroundings
system
surroundings
H > 0
H < 0
Enthalpies of Reaction
H
rxn
= H
prod
- H
react


enthalpy is an extensive property
magnitude of H depends directly on the
amount of reactant
C
(s)
+ 2H
2(g)
CH
4(g)
H = -74.8 kJ/mol
2C
(s)
+ 4H
2(g)
2CH
4(g)
H = -149.6 kJ/2mol

enthalpy change for forward rxn is equal in
magnitude but opposite in sign for the reverse rxn
CH
4(g)
C
(s)
+ 2H
2(g)
H = +74.8 kJ/mol
C
(s)
+ 2H
2(g)
CH
4(g)
H = - 74.8 kJ/mol

enthalpy change for a reaction depends on the
state of the reactants and products
C
(g)
+ 2H
2(g)
CH
4(g)
H = -793.2 kJ/mol
2H
2(g)
+ O
2(g)
2H
2
O
(g)
H = -486.6 kJ/mol
2H
2(g)
+ O
2(g)
2H
2
O
(l)
H = -571.7 kJ/mol

H
2
O
(g)

H
2
O
(l)

E
n
t
h
a
l
p
y


44 kJ
-285.8 kJ
-241.8 kJ
H = H
final
- H
initial

+

-
Practice Ex. 5.2:
Hydrogen peroxide can decompose to water and
oxygen . Calculate the value of q when 5.00 g of
H
2
O
2(l)
decomposes at constant pressure.

2H
2
O
2(l)
2H
2
O
(l)
+ O
2(g)
H = -196 kJ
5.00 g H
2
O
2(l)
x 1 mol = 0.147 mol H
2
O
2(l)

34.0 g H
2
O
2(l)

0.147 mol H
2
O
2(l)
x -196 kJ H
2
O
2(l)
= -14.4 kJ
2 mol
Calorimetry
experimental determination of H using heat
flow
heat capacity
measures the energy absorbed using
temperature change
the amount of heat required to raise its temp. by
1 K
molar heat capacity -- heat capacity of 1 mol of
substance
specific heat
heat energy required to raise some mass of a
substance to some different temp.
specific heat = quantity of heat trans.
(g substance) (temp. change)
= q .
m T
S.H. = joule
g K

q = (S.H.) (g substance) ( T)
remember: this is
change in temp.
Practice Ex. 5.3:
Calculate the quantity of heat absorbed by 50.0 kg
of rocks if their temp. increases by 12.0 C if the
specific heat of the rocks is 0.82 J/gK.
S.H. x g x T = joules

What unit should be in the solution?
joules -- quantity of heat

0.82 J x 50.0 x 10
3
g x 12.0 K = 4.9 x 10
5
J
g K
Constant-Pressure Calorimetry
H = q
p
at constant pressure as in coffee cup
calorimeter
heat gained by solution = q
soln

\ q
soln
= (S.H.
soln
)(g
soln
)(T)
heat gained by solution must that which is given
off by reaction
\

q
rxn
= - q
soln
= - (S.H.
soln
)(g
soln
)(T)
must be opposite in sign
if T is positive then q
rxn
is exothermic
Practice Ex. 5.4:
When 50.0 mL of 0.100 M AgNO
3
and 50.0 mL of
0.100 M HCl are mixed in a c.p. calorimeter, the
temp. of the mixture increases from 22.30C to
23.11C. Calculate H for this reaction, assuming
that the combined solution has a mass of 100.0 g
and a S.H. = 4.18 J/g C.

AgNO
3(aq)
+ HCl
(aq)
AgCl
(s)
+ HNO
3(aq)


q
soln
= 4.18 J x 100.0 g soln x 0.81C = 3.39 x 10
2
J
g C
q
rxn
= - q
soln
= - 3.39 x 10
2
J = - 68,000 J or
0.00500 mol - 68 kJ/mol

rxn
soln
q
insulating cup
Bomb Calorimetry (Constant-Volume)

bomb calorimeter has a pre-determined heat
capacity
sample is combusted in the calorimeter and T is
used to determine the heat change of the reaction
q
rxn
= - C
calorimeter
x T
because rxn is exothermic
heat capacity of calorimeter
rxn
water
insulation
thermometer
Practice Ex. 5.5:
A 0.5865 g sample of lactic acid, HC
3
H
5
O
3
, is
burned in a calorimeter with C = 4.812 kJ/C.
Temp. increases from 23.10C to 24.95C.
Calculate heat of combustion per gram and per
mole. T = +1.85C

q
rxn
= - (4.812 kJ/C) (1.85C) = - 8.90 kJ per
0.5865 g lactic acid
-8.90 kJ = - 15.2 kJ/g
0.5865 g

- 15.2 kJ x 90 .1 g = - 1370 kJ/mol
1 g 1 mol
Hesss Law
rxns in one step or multiple steps are additive
because they are state functions
eg.

CH
4(g)
+ 2O
2(g)
CO
2(g)
+ 2H
2
O
(g)
H = - 802 kJ




CH
4(g)
+ 2O
2(g)
CO
2(g)
+ 2H
2
O
(l)
H = - 890 kJ
2H
2
O
(g)
2H
2
O
(l)
H = - 88 kJ
Practice Ex. 5.6:
Calculate H for the conversion of graphite to
diamond:
C
graphite
C
diamond


C
graphite
+ O
2(g)
CO
2(g)
H = -393.5 kJ
C
diamond
+ O
2(g)
CO
2(g)
H = -395.4 kJ


C
graphite
+ O
2(g)
CO
2(g)
H = -393.5 kJ
CO
2(g)
C
diamond
+ O
2(g)
H = 395.4 kJ
C
graphite
C
diamond
H = + 1.9 kJ
Enthalpies of Formation
enthalpies are tabulated for many processes
vaporization, fusion, formation, etc.

enthalpy of formation describes the change in heat
when a compound is formed from its constituent
elements, H
f


standard enthalpy of formation, H
f
o
, are values for
a rxn that forms 1 mol of the compound from its
elements under standard conditions, 298 K, 1 atm
For elemental forms:
eg. C
(s)
graphite, Ag
(s)
, H
2(g)
, O
2(g)
, etc.

H
f
o
, for any element is = 0

used for calculation of enthalpies of reaction, H
rxn


H
rxn
= S H
f
o
prod
- S H
f
o
react


Practice Ex. 5.9:
Given this standard enthalpy of reaction, use the
standard enthalpies of formation to calculate the
standard enthalpy of formation of CuO
(s)(

CuO
(a)
+ H
2(g)
Cu
(s)
+ H
2
O
(l)
H
o
= -130.6 kJ

H
rxn
= S H
f
o
prod
- S H
f
o
react


-130.6 kJ = [(0) + (-285.8)] - [(CuO) + (0)]
H
f
o
CuO = -155.2 kJ/mol