Chapter5ThermochemistryChapter5Thermochemistry

Thermochemistry: relationship between

chemical reactions and energy changes
The nature of energy
Energy = ability to do work (i.e., move a mass through some
distance; w = F ×
d) or to produce heat
Two important types of energy:
-potential: energy due to
position in a field such as a
gravitational field

-kinetic: energy due to

motion

2
k
1E= mv
2
Kinetic energy
Ep stored energy with the potential to do work
Due to the position of a mass in a gravitational
field
pE= mgh
Due to the position of a charge in an electric
field
elec pot E = K qQ
r
eg: e-in the electric field of the
nucleus of an atom
This is the energy that gets
converted during chemical
reactions
k = 8.99 ×109 J m C-2.
Ep stored energy with the potential to do work
Due to the position of a mass in a gravitational
field
pE= mgh
Due to the position of a charge in an electric
field
elec pot E = K qQ
r
eg: e-in the electric field of the
nucleus of an atom
This is the energy that gets
converted during chemical
reactions
k = 8.99 ×109 J m C-2.
Chemical reaction:
Rearrangement of electrons causes energy to flow in
or out of a chemical system
Thermal energy:
Energy a substance possess due to its temperature
above the absolute zero of temperature. Associated
with the kinetic energy of atoms and molecules.
 SI Unit for energy is the joule, J:
21
2
=kEmv
1 2 -1 2 2-2
| Ek | =
| mv | =
kg·
(m s ) =
kg m s
2
J = kg m2s-2
=pE mgh
-2 2-2
| Ep | =
| mgh | =
kg ms m = kg ms
=elec pot
K qQE
r
KqQ J m C-2 C C
| E | =
|| ==
J
elec pot
r m

Example
How much energy (J) is there is one kilowatt-hour, the
unit in which power companies like Eskom bill their
customers?
Systems and Surroundings Systems and Surroundings
Thermodynamic system: that part of the universe
we are interested in.
Surroundings: the rest of the universe.

For example: C(s) + CO2(g) .

2CO(g)
System: C, CO2, CO; everything else: surroundings

Closed systems:
exchange energy but not matter with surroundings
Open systems:
exchange energy and matter with surroundings
Isolated systems:
exchange neither
Example
Identify each of the following systems as open, closed
or isolated:
Engine coolant in the cooling system of a car
Mercury in a thermometer
A living plant
Coffee in a thermos flask

Transferring Energy: Work and Heat

Transferring Energy: Work and Heat
Sir Benjamin Thompson, Count Rumford
Demonstrated the equivalence of mechanical work and heat
Transferring Energy: Work and Heat
Sir Benjamin Thompson, Count Rumford
Demonstrated the equivalence of mechanical work and heat
Workofteneitherelectricalormechanical.Mechanicalworkinvolvingexpandinggasesiscal
ledpressure-volumeworkorP-VworkTransferring Energy: Work and Heat
piston
reaction chamber
SYSTEM:
C2H5OH(g) + 3O2(g) .
2CO2(g) + 2H2O(g) +
energy
heat flows from a
hot body to cold
surroundings
mechanical work
done
ENERGY:
ability to do WORK and/or to
TRANSFER HEAT
TheFirstLawofThermodynamics
Energy cannot be created or destroyed, but
merely converted from one form to another
If
a
piece
of
metal
at
85°C
is
added
to
water
at
25°C,
the
final
temperature
of
the
system
is
30°C.
Which
of
the
following
is
true?

1.
Heat
lost
by
the
metal
>
heat
gained
by
water
2.
Heat
gained
by
water
>
heat
lost
by
the
metal
3.
Heat
lost
by
metal
>
heat
lost
by
the
water
4.
Heat
lost
by
the
metal
=
heat
gained
by
water
5.
More
information
is
required.
Internal Energy, U (textbook uses E)
Sum of all Ek and Ep of a system
Motion of molecules
Motion of electrons
Position of electrons in electrostatic field of the nucleus
Interactions between molecules, etc.
Virtually impossible to determine or calculate U
During a chemical reaction can only determine changes in U
.U = Ufinal -Uinitial
The quantity .U can be measured
Virtually impossible to determine or calculate U
During a chemical reaction can only determine changes in U
.U = Ufinal -Uinitial
The quantity .U can be measured
Two ways for energy to be transferred:
Heat (q) Work (w)
SystemSystem
q q
w w
+
work done on the system work done by the system
.U = q + w
So... So...
Example
The battery does 555 kJ of work
every hour driving the pump. The
system loses 124 kJ of energy per
hour to the surroundings.
X
system What is .Usystem per hour?
Exothermic and Endothermic Processes
Endothermic: absorbs heat from the surroundings.
Exothermic: transfers heat to the surroundings.
Note:

An exothermic reaction (q<0) feels hot.

An endothermic reaction (q>0) feels cold
Example

Length of arrow = relative magnitude of energy transferred

Which of these processes is exothermic?
For which (if any) is .U < 0?
For which (if any) is there a net gain of internal energy?
U is a state function
State functions depend only on the current state of the
system and not how the internal energy was used to get
there. (State functions do not depend on path.)
U is a state function
State functions depend only on the current state of the
system and not how the internal energy was used to get
there. (State functions do not depend on path.)
q and w are path functions

Same T, P, n
.U s the same
system 2
H2O
system 1
H2O
q
w
.U
+50 kJ then +10 kJ then
-20 kJ -15 kJ
-10 kJ then +60 kJ then
+25 kJ -10 kJ
+45 kJ +45 kJ
(q = +30 kJ (q = -5 kJ
w = +15 kJ) w = +50 kJ)
Many chemical systems expand or contract when they
react. These systems are doing expansion(PV) work.
Heat
CaCO3
expanding CO2
Many chemical systems expand or contract when they
react. These systems are doing expansion(PV) work.
Heat
CaCO3
expanding CO2
Expansion work done by a gas
.h

15
w = -P.V
Haveoppositesignsbecausewhengasexpands(.V>0),systemdoeswork(w<0)Palwaysreferstot
heexternalpressure thepressurethatcausesacompressionorresistsanexpansion
Example
A 10.0 W heater heats gas in a cylinder for 1 min. The
cylinder s volume expands from 1.00 l to 1.50 l. Calculate
.U for the gas if Patm = 0.965 atm.

Measuring .U
.U = q + w
= q -P.V
If the reaction is carried out in a sealed rigid container, .V = 0
.U = qV
The change in internal energy of a system is equal to the
heat transferred to or from the system at constant volume
Most reactions carried our under constant pressure
Definition
Define a new state function called the ENTHALPY of
the system, H, such that
H = U + PV
As for U, it is virtually impossible to measure or to
calculate H, only .H. Under constant P conditions
.H = .U + P.V
Most reactions carried our under constant pressure
Definition
Define a new state function called the ENTHALPY of
the system, H, such that
H = U + PV
As for U, it is virtually impossible to measure or to
calculate H, only .H. Under constant P conditions
.H = .U + P.V
Measuring .H
.H = .U + P.V
= q + w + P.V
= q P.V + P.V
= qP
.H = qP
ThechangeinenthalpyofasystemhasnoeasilyinterpretedmeaningexceptatconstantPwherei
tisequaltotheenergyflowasheatForaprocesscarriedutatconstantP,whereonly PV workisallo
wed:
At constant P, exothermic means .H < 0 and
endothermic means .H > 0
Which of the following statements is/are true for the
diagram?
1. .U > 0
2. .U < 0
3. .H > 0
4. .H < 0
5. .H = .U
Heat
Work
Pisconstant

Examples
1. For a reaction at constant P, .U = -65 kJ and 28 kJ
expansion work is done by the system. What is .H?
2. For a reaction .H = -15 kJ and 22 kJ expansion work
is done on the system. What is .U?
Example
Which will have the higher enthalpy (same T unless
otherwise indicated)?
1 mol CO2(g) or 1 mol CO2(s)
2 mol of H atoms or 1 mol of H2 molecules
1 mol H2(g) and 0.5 mol O2(g) or 1 mol H2O?
1 mol N2(g) at 100 oC or 1 mol N2(g) at 300 oC?
Measuring heat flows: Calorimetry
reaction
chamber
water bath
thermometer
T increases for an exothermic reaction and decreases for
an endothermic one
Need to relate q to .T
Heat capacity, C
heat suppliedC =
change in temperature
qC =
T.JJKJ KJ K-1K-1
Need to relate q to .T
Heat capacity, C
heat suppliedC =
change in temperature
qC =
T.JJKJ KJ K-1K-1
Which
metal
will
undergo
the
greatest
temperature
change
if
an
equal
amount
of
heat
is
added
to
each?

1.
Fe,
Cm
=
0.45
J/g
K
2.
Al,
Cm
=
0.90
J/g
K
3.
Cu,
Cm
=
0.38
J/g
K
4.
Pb,
Cm
=
0.13
J/g
K
5.
Sn,
Cm
=
0.22
J/g
K
Recall that size of 1 degree Kelvin = size of 1 degree centigrade
.T (K) = .T (oC)
reaction
chamber
water bath
thermometer
.T will depend on the quantity of
water; so more common to use the
intensive property:
SPECIFIC HEAT CAPACITY Cs; or
MOLAR HEAT CAPCITY Cm

Cs
J K-1 g-1J K-1 g-1
Cm
J K-1 mol-1J K-1 mol-1
q = m Cs/m .T
JJg or
molsg or
mols J K-1 g-1
or
J K-1 mol-1
J K-1 g-1
or
J K-1 mol-1
KK
Example
The molar heat capacity of water is 75.4 J K-1 mol-1. How long
must a 1.000 kW heater run to raise the temperature of 500.0 g
of water from 20.0 oC to 80.0 oC?
Strategy
Mass mols energy time
Example
The molar heat capacity of water is 75.4 J K-1 mol-1. How long
must a 1.000 kW heater run to raise the temperature of 500.0 g
of water from 20.0 oC to 80.0 oC?
Strategy
Mass mols energy time
Reaction is open to the
atmosphere
qP = .H
and we measure reaction
enthalpy
Reaction occurs under
constant volume conditions
qV = .U
and we measure change in
internal energy
p. 186 10th Ed
Reaction occurs under
constant volume conditions
qV = .U
and we measure change in
internal energy
p. 186 10th Ed
Example
When 100 ml of an aqueous solution of certain reactants
are mixed, it is known that their reaction releases 1.78 kJ of
energy.
When this reaction occurred in an open calorimeter, the
temperature rose by 3.65 oC.

Next 50 ml HCl was mixed with 50 ml NaOH in the same

calorimeter; in this case the temperature rise was 1.26 oC.

What is the heat output of the neutralisation reaction?

Example
A 2.200 g sample of quinone (C6H4O2) is burned in a bomb
calorimeter with a heat capacity of 7.854 kJ K-1.
The temperature of the calorimeter increases from 23.44 to
30.57 oC.
What is the molar heat of combustion of quinone?
Enthalpies of Reaction
final initial
products reactants
.H = H - H
= H - H
For a reaction:
Enthalpy is an extensive property (magnitude of .H is directly
proportional to amount):
CH4(g) + 2O2(g) .CO2(g) + 2H2O(g) .H = -802 kJ mol-1
2CH4(g) + 4O2(g) .2CO2(g) + 4H2O(g) .H = -1604 kJ mol-1
kJ mol-1 for the reaction as written
For the reverse reaction the sign of .H changes:
CO2(g) + 2H2O(g) .
CH4(g) + 2O2(g) .H = +802 kJ mol-1
Values of .H depend on conditions such as pressure and
physical state of reactants and products.
Therefore define the standard enthalpy of reaction .Ho as
enthalpy change that occurs when the reaction is under
standard thermodynamic conditions
Pressure: 1 atmosphere
Temp: 25 oC

If a reaction is carried out in a number of steps, .H for the

overall reaction is the sum of .H for each individual step.
This is known as Hess Law. It is merely a consequence of the
First Law of Thermodynamics.
.H1 = .H2 + .H3
What is the value of the unknown .H in the diagram?
1. +329.5 kJ
2. -329.5 kJ
3. +285.8 kJ
4. -241.8 kJ
5. +241.8 kJ
Most useful application of Hess Law:
Use extensive data available for heats of combustions
to determine .H for other reactions
Example
Given:
C3H8(g) + 5O2(g) .
3CO2(g) + 4H2O(l) .Ho = -2220 kJ mol-1
C(s) + O2(g) .
CO2(g) .Ho = -394 kJ mol-1
H2(g) + ½O2(g) .
H2O(l) .Ho = -286 kJ mol-1
Calculate .Ho for:
3C(s) + 4H2(g) .
C3H8(g)
Standard Enthalpies of Formation Standard Enthalpies of Formation
Definition
If 1 mol of compound is formed from its constituent
elements in their standard states, then the enthalpy
change for the reaction is called the standard
enthalpy of formation, .Hof .
Corollary
Standard enthalpy of formation of the most stable
form of an element is zero.

p. 192 in 10th Ed. See also Appendix C

Whichreactionrepresentsthe .HfreactionforNaNO3?
Whichreactionrepresentsthe .HfreactionforNaNO3?
Usefulness?
We use Hess Law to calculate enthalpies of a
reaction from enthalpies of formation
For any reaction:
( ) ( )
.=-
=.-.SSSo o o
rxn final initial
o o
f f
H H H
n H prod n H react
stoichiometriccoefficientsstoichiometric
coefficients
Example
Calculate .Ho for the combustion of 1 mol of acetylene C2H2.

Let s see how we have used Hess Law to get this result
Integrated Exercise
Combustion of a hydrocarbon produces 21.83 g of
CO2, 4.47 g of H2O and 311 kJ of heat.
(i)
What mass of hydrocarbon was
combusted?
(ii) What is its empirical formula?
(iii) Calculate .Hof per empirical formula unit for
the hydrocarbon
End of Chapter 5:
Thermochemistry