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THERMOCHEMISTRY 1

Thermodynamics
The study of Heat and Work
and State Functions
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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
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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
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These reactions are PRODUCT FAVORED


They proceed almost completely from
reactants to products, perhaps with
some outside assistance.
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Energy & 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


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Potential
Potential &
& Kinetic
Kinetic Energy
Energy
Potential energy
energy a
motionless
body has by
virtue of its
position.
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Potential Energy
on the Atomic 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.
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Potential Energy
on the Atomic Scale
Positive and
negative particles
(ions) attract one
another.
Two atoms can
bond
As the particles
attract they have a
lower potential
energy
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Potential
Potential &
& Kinetic
Kinetic Energy
Energy
Kinetic energy
energy of
motion
Translation
Potential
Potential &
& Kinetic
Kinetic Energy
Energy
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Kinetic energy
energy of
motion.
rotate
rotate
vibrate
vibrate
translate
translate
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Internal Energy (E)


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


PE + KE = Internal energy (E or U)

QuickTime and a
Graphics decompressor
are needed to see this picture.
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Internal Energy (E)


The higher the T
the higher the
internal energy
So, use changes
in T (T) to
monitor changes
in E (E).
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Thermodynamics
Thermodynamics is the science of heat
(energy) transfer.

Heat energy is associated


with molecular motions.
Heat transfers until thermal equilibrium is
established.
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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
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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
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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.
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Energy Change in
Chemical 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
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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
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HEAT CAPACITY
The heat required to raise an
objects T by 1 C.

Which has the larger heat capacity?


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

Aluminum
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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)
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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/gK)(25.0 g)(37 - 310)K
q = - 6120 J
Noticethatthenegativesignonqsignals
heatlostbyortransferredOUTofAl.
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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)
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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 + energy
swimming
b) you use water to put
out a fire.
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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
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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/gK
J/gK
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
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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/gK)(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 10 6 J = 1510 kJ
Chemical Reactivity
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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
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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.


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Heat Energy Transfer in


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

Heat transfers from surroundings to system in endothermic process.


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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.
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Energy Level Diagram


for Heat Energy
Transfer

CO2 gas

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

CO2 solid
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Heat Energy Transfer in


Physical 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.
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FIRST LAW OF
THERMODYNAMICS
heat energy transferred

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

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

SYSTEM

E = q + w

w transfer in w transfer out


(+w) (-w)
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ENTHALPY
Most chemical reactions occur at constant P, so

HeattransferredatconstantP=qpp

qpp=H whereH=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
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ENTHALPY
H = Hfinal - Hinitial

IfIf H
Hfinal > H initial then H
then H is
is positive
final > Hinitial positive
Process is ENDOTHERMIC
Process is ENDOTHERMIC

IfIf H
Hfinal < H initial then H
then H is
is negative
final < Hinitial negative
Process is EXOTHERMIC
Process is EXOTHERMIC
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USING 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 ENTHALPY
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Making liquid H2O from H2 +


O2 involves two exothermic
steps.
H2 + O2 gas

H2O vapor Liquid H2O


USING ENTHALPY
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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 HESSS LAW
If a rxn. is the sum of 2 or more
others, the net H is the sum of the
Hs of the other rxns.
Hesss Law
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& 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.
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Hesss 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.
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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.
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Standard Enthalpy 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 Values
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Dependon
Dependonhowthereactioniswritten
howthereactioniswrittenandonphases
andonphases
ofreactantsandproducts
ofreactantsandproducts
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
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Standard Enthalpy Values


NIST (Natl 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 Hs to calculate enthalpy change for

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

(product is called water gas)


Using Standard Enthalpy Values
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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)
H
Hoonet = +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 ENDOthermic.
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Using Standard Enthalpy Values

Calculate H of
reaction?

In general, when ALL


enthalpies of formation are
known:

Hoo
H rxn = H oo
(products) H oo
(reactants)
rxn = Hff (products) Hff (reactants)
Remember that always = final initial
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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)
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Using Standard Enthalpy Values

CH3OH(g)+3/2O2(g)>CO2(g)+2H2O(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
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Measuring Heats of Reaction


Constant Volume
Bomb Calorimeter
Burn combustible
sample.
Measure heat evolved
in a reaction.
Derive E for
reaction.
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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


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

Step 2Calc. heat transferred from reaction to bomb.


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

Step 3Total heat evolved


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