THERMOCHEMISTRY

THERMOCHEMISTRY 1

Thermodynamics
Thermodynamics
The
The study
study of
of Heat
Heat and
and Work
Work
and
and State
State Functions
Functions
 2

Energy
Energy &
& Chemistry
Chemistry
ENERGY is the capacity to do
work or transfer heat.
HEAT is the form of energy that
flows between 2 objects
because of their difference in
temperature.
Other forms of energy —
• light
• electrical
• kinetic and potential
 3

Energy & Chemistry

• Burning peanuts supply sufficient energy

to boil a cup of water. • Burning sugar
(sugar reacts with
KClO3, a strong
oxidizing agent)
 Energy & Chemistry
4

• These reactions are PRODUCT FAVORED

• They proceed almost completely from
reactants to products, perhaps with some
outside assistance.
 5

Energy
Energy &
& Chemistry
Chemistry
2 H2(g) + O2(g) -->
2 H2O(g) + heat and light
This can be set up to provide
ELECTRIC ENERGY in a fuel
cell.
Oxidation:
2 H2 ---> 4 H+ + 4 e-

Reduction:
4 e- + O2 + 2 H2O ---> 4 OH-

CCR, page 845

 6

Potential
Potential &
& Kinetic
Kinetic Energy
Energy
Potential
energy —
energy a
motionless
body has by
virtue of its
position.
 7
Potential
Potential Energy
Energy
on
on the
the Atomic
Atomic Scale
Scale
• Positive and
negative particles
(ions) attract one
another.
• Two atoms can
bond
• As the particles
attract they have a
lower potential
energy NaCl — composed of
Na+ and Cl- ions.
 8
Potential
Potential Energy
Energy
on
on the
the Atomic
Atomic Scale
Scale
• Positive and
negative particles
(ions) attract one
another.
• Two atoms can
bond
• As the particles
attract they have a
lower potential
energy
 9

Potential
Potential &
& Kinetic
Kinetic Energy
Energy
Kinetic energy
— energy of
motion
• Translation
 Potential
Potential &
& Kinetic
Kinetic Energy
Energy
10

Kinetic energy
— energy of
motion.
rotate
rotate
vibrate
vibrate
translate
translate
 11

Internal
Internal Energy
Energy (E)
(E)
• PE + KE = Internal energy (E or U)
• Int. E of a chemical system
depends on
• number of particles
• type of particles
• temperature
 12

Internal
Internal Energy
Energy (E)
(E)
• PE + KE = Internal energy (E or U)

QuickTime™ and a
Graphics decompressor
are needed to see this picture.
 13

Internal
Internal Energy
Energy (E)
(E)
• The higher the T
the higher the
internal energy
• So, use changes
in T (∆T) to
monitor changes
in E (∆E).
 14

Thermodynamics
Thermodynamics
• Thermodynamics is the science of heat
(energy) transfer.

Heat energy is associated

with molecular motions.
Heat transfers until thermal equilibrium is
established.
 15
Directionality of Heat Transfer
• Heat always transfer from hotter object to
cooler one.
• EXOthermic: heat transfers from SYSTEM to
SURROUNDINGS.

T(system) goes down

T(surr) goes up
 16
Directionality of Heat Transfer
• Heat always transfer from hotter object to
cooler one.
• ENDOthermic: heat transfers from
SURROUNDINGS to the SYSTEM.

T(system) goes up
T (surr) goes down
 17

Energy
Energy &
& Chemistry
Chemistry
All of thermodynamics depends
on the law of
CONSERVATION OF ENERGY.
• The total energy is unchanged in
a chemical reaction.
• If PE of products is less than
reactants, the difference must be
released as KE.
 18

Energy
Energy Change
Change in
in
Chemical
Chemical Processes
Processes
PE

Reactants
Kinetic 
Energy

Products

PE of system dropped. KE increased. Therefore,

you often feel a T increase.
 UNITS
UNITS OF
OF ENERGY
ENERGY
19

1 calorie = heat required to

raise temp. of 1.00 g of H2O
by 1.0 oC.
1000 cal = 1 kilocalorie = 1
kcal
1 kcal = 1 Calorie (a food
“calorie”)
But we use the unit called the
JOULE
1 cal = 4.184 joules James Joule
1818-1889
 20

HEAT CAPACITY
The heat required to raise an
object’s T by 1 ˚C.

Which has the larger heat capacity?

 21
Specific
Specific Heat
Heat Capacity
Capacity
How much energy is transferred due to T difference?
The heat (q) “lost” or “gained” is related to
a) sample mass
b) change in T and
c) specific heat capacity

Specific heat capacity

=
heat lost or gained by substance (J)
(mass,g)(T change,K)
 Specific
Specific Heat
Heat Capacity
22

Capacity
Substance Spec. Heat (J/g•K)
H2O 4.184
Ethylene glycol 2.39
Al 0.897
glass 0.84

Aluminum
 23

Specific
Specific Heat
Heat Capacity
Capacity
If 25.0 g of Al cool from
310 oC to 37 oC, how
many joules of heat
energy are lost by
the Al?

Specific heat capacity

=
heat lost or gained by substance (J)
(mass, g)(T change,K)
 24

Specific
Specific Heat
Heat Capacity
Capacity
If 25.0 g of Al cool from 310 oC to 37 oC, how many joules of heat energy are lost by the Al?

heat gain/lose = q = (sp. ht.)(mass)(∆T)

where ∆T = Tfinal - Tinitial

q = (0.897 J/g•K)(25.0 g)(37 - 310)K
q = - 6120 J
 Notice that the negative sign on q signals 
heat “lost by” or transferred OUT of Al.
 25
Heat Transfer
No Change in State
q transferred = (sp. ht.)(mass)(∆T)
 Heat
Heat Transfer
Transfer with
with 26

Change
Change of
of State
State
Changes of state involve energy (at constant T)
Ice + 333 J/g (heat of fusion) -----> Liquid water
q = (heat of fusion)(mass)
 27

Heat
Heat Transfer
Transfer and
and
Changes
Changes of
of State
State
Liquid ---> Vapor
Requires energy (heat).
This is the reason
a) you cool down after
swimming + energy

b) you use water to put

out a fire.
 28
Heating/Cooling
Heating/Cooling Curve
Curve for
for Water
Water

Evaporate water

Heat water

Melt ice
Note that T is
constant as ice melts
 Heat
Heat &
& Changes
Changes of
of State
29
State
What quantity of heat is required to
melt 500. g of ice and heat the
water to steam at 100 oC?

Heat
Heat of
of fusion
fusion of
of ice
ice == 333
333 J/g
J/g
Specific
Specific heat
heat of
of water
water == 4.2
4.2 J/g•K
J/g•K
Heat
Heat of
of vaporization
vaporization == 2260
2260 J/g
J/g

+333 J/g +2260 J/g

 Heat
Heat &
& Changes
Changes of
of State
30
State
How much heat is required to melt 500. g of ice
and heat the water to steam at 100 oC?
1. To melt ice
q = (500. g)(333 J/g) = 1.67 x 105 J
2. To raise water from 0 oC to 100 oC
q = (500. g)(4.2 J/g•K)(100 - 0)K = 2.1 x 105 J
3. To evaporate water at 100 oC
q = (500. g)(2260 J/g) = 1.13 x 106 J
4. Total heat energy = 1.51 x 106 J = 1510
kJ
 Chemical
31

Chemical Reactivity
Reactivity
What drives chemical reactions? How do
they occur?
The first is answered by THERMODYNAMICS
and the second by KINETICS.
Have already seen a number of “driving
forces” for reactions that are PRODUCT-
FAVORED.
• formation of a precipitate
• gas formation
• H2O formation (acid-base reaction)
• electron transfer in a battery
 Chemical Reactivity
32

But energy transfer also allows us to

predict reactivity.
In general, reactions that transfer energy
to their surroundings are product-
favored.

So, let us consider heat transfer in chemical

processes.
 33

Heat Energy Transfer in

a Physical Process
CO2 (s, -78 oC) ---> CO2 (g, -78 oC)

Heat transfers from surroundings to system in endothermic process.

 34

Heat Energy Transfer in

a Physical Process
• CO2 (s, -78 oC) --->
CO2 (g, -78 oC)
• A regular array of
molecules in a
solid
-----> gas phase
molecules.
• Gas molecules
have higher kinetic
energy.
 35

Energy Level Diagram

for Heat Energy
Transfer

CO2 gas

∆E = E(final) - E(initial)
= E(gas) - E(solid)

CO2 solid
 36

Heat
Heat Energy
Energy Transfer
Transfer in
in
Physical
Physical Change
Change
CO2 (s, -78 oC) ---> CO2 (g, -78 oC)
Two things have happened!
• Gas molecules have higher kinetic
energy.
• Also, WORK is done by the system
in pushing aside the atmosphere.
 37

FIRST
FIRST LAW
LAW OF
OF
THERMODYNAMICS
THERMODYNAMICS
heat energy transferred

∆E = q + w work done
by the
energy system
change

Energy is conserved!
 38
heat transfer in heat transfer out
(endothermic), +q (exothermic), -q

SYSTEM
SYSTEM
∆E = q + w

w transfer in w transfer out

(+w) (-w)
 39

ENTHALPY
ENTHALPY
Most chemical reactions occur at constant P, so

Heat transferred at constant P = qpp

qpp =   ∆H  where H  =  enthalpy

and so ∆E = ∆H + w (and w is usually small)

∆H = heat transferred at constant P ≈ ∆E
∆H = change in heat content of the system
∆H = Hfinal - Hinitial
 40

ENTHALPY
ENTHALPY
∆H = Hfinal - Hinitial

If H
If Hfinal > H initial then
final > Hinitial then ∆H
∆H is
is positive
positive
Process is ENDOTHERMIC
Process is ENDOTHERMIC

If H
If Hfinal < H initial then
final < Hinitial then ∆H
∆H is
is negative
negative
Process is EXOTHERMIC
Process is EXOTHERMIC
 41

USING
USING ENTHALPY
ENTHALPY
Consider the formation of water
H2(g) + 1/2 O2(g) --> H2O(g) + 241.8 kJ

Exothermic reaction — heat is a

“product” and ∆H = – 241.8 kJ
 USING
USING ENTHALPY
ENTHALPY
42

Making liquid H2O from H2

+ O2 involves two
exothermic steps.
H2 + O2 gas

H2O vapor Liquid H2O

 USING ENTHALPY
43

Making H2O from H2 involves two steps.

H2(g) + 1/2 O2(g) ---> H2O(g) + 242 kJ
H2O(g) ---> H2O(liq) + 44 kJ
-----------------------------------------------------------------------

H2(g) + 1/2 O2(g) --> H2O(liq) + 286 kJ

Example of HESS’S LAW—
If a rxn. is the sum of 2 or more others,
the net ∆H is the sum of the ∆H’s of the
other rxns.
 Hess’s Law
44

& Energy Level Diagrams

Forming H2O can occur in a

single step or in a two
steps.

∆Htotal is the same no matter

which path is followed.
 45
Hess’s Law
& Energy Level Diagrams

Forming CO2 can occur in a

single step or in a two steps.

∆Htotal is the same no matter

which path is followed.
 46


∆∆HH along
along one
one path
path ==

∆∆HH along
along another
another path
path

• This equation is valid because

∆H is a STATE FUNCTION
• These depend only on the state
of the system and not on how
the system got there.
• V, T, P, energy — and your bank
account!
• Unlike V, T, and P, one cannot
measure absolute H. Can only
measure ∆H.
 47

Standard
Standard Enthalpy
Enthalpy Values
Values
Most ∆H values are labeled ∆Ho
Measured under standard conditions
P = 1 bar = 105 Pa = 1 atm /
1.01325 Concentration = 1
mol/L
T = usually 25 oC
with all species in standard states
e.g., C = graphite and O2 = gas
 Enthalpy
Enthalpy Values
Values
48

Depend on 
Depend on how the reaction is written
how the reaction is written and on phases 
 and on phases 
of reactants and products
of reactants and products
H2(g) + 1/2 O2(g) --> H2O(g)
∆H˚ = -242 kJ
2 H2(g) + O2(g) --> 2 H2O(g)
∆H˚ = -484 kJ
H2O(g) ---> H2(g) + 1/2 O2(g)
∆H˚ = +242 kJ
H2(g) + 1/2 O2(g) --> H2O(liquid)
∆H˚ = -286 kJ
 49

Standard Enthalpy Values

NIST (Nat’l Institute for Standards and
Technology) gives values of
∆Hfo = standard molar enthalpy of
formation
— the enthalpy change when 1 mol of
compound is formed from elements
under standard conditions.
See Table 6.2
∆Hf , standard molar
o 50

enthalpy of formation
Enthalpy change when 1 mol of compound
is formed from the corresponding
elements under standard conditions
H2(g) + 1/2 O2(g) --> H2O(g)
∆Hfo (H2O, g)= -241.8 kJ/mol
By definition,
∆Hfo = 0 for elements in their standard states.
 Using Standard Enthalpy Values 51

Use ∆H˚’s to calculate enthalpy change for

H2O(g) + C(graphite) --> H2(g) + CO(g)

(product is called “water gas”)

 Using Standard Enthalpy Values
52

H2O(g) + C(graphite) --> H2(g) + CO(g)

From reference books we find

• H2(g) + 1/2 O2(g) --> H2O(g) ∆Hf˚ = - 242

kJ/mol

• C(s) + 1/2 O2(g) --> CO(g) ∆Hf˚ = - 111

kJ/mol
 Using Standard Enthalpy Values 53

H2O(g) --> H2(g) + 1/2 O2(g) ∆Ho = +242 kJ

C(s) + 1/2 O2(g) --> CO(g) ∆Ho = -111 kJ
--------------------------------------------------------------------------------

H
H22O(g)
O(g) +
+ C(graphite)
C(graphite) -->--> H
H22(g)
(g) +
+ CO(g)
CO(g)
∆
∆HHoonet = +131 kJ
net = +131 kJ

To convert 1 mol of water to 1 mol each

of H2 and CO requires 131 kJ of energy.
The “water gas” reaction is
 54

Using Standard Enthalpy Values

Calculate ∆H of
reaction?

In general, when ALL

enthalpies of formation are
known:

∆∆H
H rxn
oo
 =   ∆H (products)  ­     ∆H (reactants)
rxn  =   ∆Hff    (products)  ­     ∆Hff    (reactants)
 oo
 oo

Remember that ∆ always = final – initial

 55

Using Standard Enthalpy Values

Calculate the heat of combustion of

methanol, i.e., ∆Horxn for
CH3OH(g) + 3/2 O2(g) --> CO2(g) + 2 H2O(g)
∆Horxn =  ∆Hfo (prod) -  ∆Hfo (react)
 56
Using Standard Enthalpy Values

CH3OH(g) + 3/2 O2(g) ­­> CO2(g) + 2 H2O(g)
 ∆Horxn =   ∆Hfo (prod) ­    ∆Hfo (react)

∆Horxn = ∆Hfo (CO2) + 2 ∆Hfo (H2O)

- {3/2 ∆Hfo (O2) + ∆Hfo (CH3OH)}
= (-393.5 kJ) + 2 (-241.8 kJ)
- {0 + (-201.5 kJ)}
∆Horxn = -675.6 kJ per mol of methanol
 CALORIMETRY
CALORIMETRY
57

Measuring Heats of Reaction

Constant Volume
“Bomb” Calorimeter
• Burn combustible
sample.
• Measure heat evolved
in a reaction.
• Derive ∆E for
reaction.
 58
Calorimetry

Some heat from reaction warms

water
qwater = (sp. ht.)(water mass)(∆T)

Some heat from reaction warms

“bomb”
qbomb = (heat capacity, J/K)(∆T)

Total heat evolved = qtotal = qwater + qbomb

 59
Measuring
Measuring Heats
Heats of
of Reaction
Reaction
CALORIMETRY
CALORIMETRY

Calculate heat of combustion of octane.

C8H18 + 25/2 O2 --> 8 CO2 + 9 H2O
• Burn 1.00 g of octane
• Temp rises from 25.00 to 33.20 oC
• Calorimeter contains 1200 g water
• Heat capacity of bomb = 837 J/K
 Measuring
Measuring Heats
Heats of
of Reaction
Reaction 60

CALORIMETRY
CALORIMETRY
Step 1 Calc. heat transferred from reaction to water.
q = (4.184 J/g•K)(1200 g)(8.20 K) = 41,170 J

Step 2 Calc. heat transferred from reaction to bomb.

q = (bomb heat capacity)(∆T)
= (837 J/K)(8.20 K) = 6860 J

Step 3 Total heat evolved

41,170 J + 6860 J = 48,030 J
Heat of combustion of 1.00 g of octane = - 48.0 kJ