Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
THERMOCHEMISTRY
Thermodynamics
The study of Heat and Work
and State Functions
Energy
Energy &
& Chemistry
Chemistry
ENERGY is the capacity to
Burning sugar
(sugar reacts with
KClO3, a strong
oxidizing agent)
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.
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.
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
Potential
Potential &
& Kinetic
Kinetic Energy
Energy
Kinetic energy
energy of
motion
Translation
Potential
Potential &
& Kinetic
Kinetic Energy
Energy
Kinetic energy
energy of
motion.
rotate
rotate
vibrate
vibrate
translate
translate
10
11
12
QuickTime and a
Graphics decompressor
are needed to see this picture.
13
Thermodynamics
Thermodynamics is the science of heat
(energy) transfer.
14
15
T(system) goes up
T (surr) goes down
16
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.
17
PE
Energy Change in
Chemical Processes
Reactants
Kinetic
Energy
Products
18
UNITS
UNITS OF
OF ENERGY
ENERGY
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
19
20
HEAT CAPACITY
The heat required to raise an
objects T by 1 C.
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)
21
Specific
Specific Heat
Heat Capacity
Capacity
Substance
Spec. Heat (J/gK)
H2O
4.184
Ethylene glycol
2.39
Al
0.897
glass
0.84
Aluminum
22
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)
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?
q = - 6120 J
Noticethatthenegativesignonqsignals
heatlostbyortransferredOUTofAl.
24
Heat Transfer
No Change in State
q transferred = (sp. ht.)(mass)(T)
25
Heat
Heat Transfer
Transfer with
with
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)
26
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
b) you use water to put
out a fire.
+ energy
Heating/Cooling
Heating/Cooling Curve
Curve for
for Water
Water
Evaporate water
Heat water
Melt ice
Note that T is
constant as ice melts
28
Heat
Heat &
& Changes
Changes of
of State
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
29
Heat
Heat &
& Changes
Changes of
of State
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
30
Chemical 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
31
Chemical Reactivity
32
33
34
E = E(final) - E(initial)
= E(gas) - E(solid)
CO2 solid
35
36
FIRST LAW OF
THERMODYNAMICS
heat energy transferred
E = q + w
energy
change
work done
by the
system
Energy is conserved!
37
38
heat transfer in
(endothermic), +q
SYSTEM
E = q + w
w transfer in
(+w)
w transfer out
(-w)
ENTHALPY
Most chemical reactions occur at constant P, so
HeattransferredatconstantP=qpp
qpp=H
whereH=enthalpy
H = Hfinal - Hinitial
39
ENTHALPY
H = Hfinal - Hinitial
IfIf H
> H initial then
Hfinal
then
H
H is
is positive
positive
final > Hinitial
Process
Process is
is ENDOTHERMIC
ENDOTHERMIC
IfIf H
< H initial then
Hfinal
then
H
H is
is negative
negative
final < Hinitial
Process
Process is
is EXOTHERMIC
EXOTHERMIC
40
USING ENTHALPY
Consider the formation of water
41
USING ENTHALPY
42
H2O vapor
Liquid H2O
USING ENTHALPY
Making H2O from H2 involves two steps.
H2(g) + 1/2 O2(g) ---> H2O(g) + 242 kJ
H2O(g) ---> H2O(liq) + 44 kJ
-----------------------------------------------------------------------
43
Hesss Law
& 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.
44
Hesss Law
& Energy Level Diagrams
45
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.
46
47
Enthalpy Values
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
48
49
Hf , standard molar
enthalpy of formation
o
50
51
52
Hf = - 111 kJ/mol
H
H22O(g)
O(g) ++ C(graphite)
C(graphite) -->
--> H
H22(g)
(g) ++ CO(g)
CO(g)
= +131 kJ
H
Hoonet
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.
53
54
oo
oo
oo
H
=
H
(products)
H
(reactants)
H rxn
rxn = Hff (products) Hff (reactants)
55
56
CALORIMETRY
57
Calorimetry
58
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
59
Measuring
Measuring Heats
Heats of
of Reaction
Reaction
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
60
61
Thank
Thank You
You