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Thermodynamics
The study of Heat and Work
and State 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
Reduction:
4 e- + O2 + 2 H2O ---> 4 OH-
Potential
Potential &
& Kinetic
Kinetic Energy
Energy
Potential energy
energy a
motionless
body has by
virtue of its
position.
7
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.
8
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
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
QuickTime and a
Graphics decompressor
are needed to see this picture.
13
Thermodynamics
Thermodynamics is the science of heat
(energy) transfer.
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 Change in
Chemical Processes
PE
Reactants
Kinetic
Energy
Products
HEAT CAPACITY
The heat required to raise an
objects T by 1 C.
Capacity
Substance Spec. Heat (J/gK)
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
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?
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 + energy
swimming
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
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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
CO2 gas
E = E(final) - E(initial)
= E(gas) - E(solid)
CO2 solid
36
FIRST LAW OF
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
E = q + w
ENTHALPY
Most chemical reactions occur at constant P, so
HeattransferredatconstantP=qpp
qpp=H whereH=enthalpy
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
41
USING ENTHALPY
Consider the formation of water
H2(g) + 1/2 O2(g) --> H2O(g) + 241.8 kJ
HH along
along one
one path
path ==
HH along
along another
another path
path
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
49
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
H
H22O(g)
O(g) ++ C(graphite)
C(graphite) -->--> H
H22(g)
(g) ++ CO(g)
CO(g)
H
Hoonet = +131 kJ
net = +131 kJ
Calculate H of
reaction?
Hoo
H rxn = H oo
(products) H oo
(reactants)
rxn = Hff (products) Hff (reactants)
Remember that always = final initial
55
CH3OH(g)+3/2O2(g)>CO2(g)+2H2O(g)
Horxn= Hfo(prod) Hfo(react)
CALORIMETRY
CALORIMETRY
Step 1Calc. heat transferred from reaction to water.
q = (4.184 J/gK)(1200 g)(8.20 K) = 41,170 J