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Chapter 5
Thermochemistry
Thermochemistry:
Relationships between chemical reactions
and energy changes
Thermodynamics:
Therm: heat
Dynamics: power
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Energy
Energy: the capacity to do work
Radiant energy
Thermal energy
Chemical energy
Nuclear energy
900C
Coffee cup?
900C
Bathtub?
4
900C
What additional
information is
needed?
400C
Energy Changes
The system is the specific part of the universe that is of
interest in the study.
SYSTEM
SURROUNDINGS
open
Exchange: mass & energy
closed
isolated
energy
nothing
Energy Changes
Enthalpy
Exothermic process: is any process that gives off heat
transfers thermal energy from the system to the surroundings.
2H2 (g) + O2 (g)
H2O (g)
Enthalpy
Enthalpy: a thermodynamic quantity used to
H = E + PV
Equation:
Hreaction = Hproducts - Hreactants
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Enthalpy: Examples
Indicate the sign of enthalpy change in the
following processes carried under atmospheric
pressure, and indicate whether the process is
exothermic or endothermic:
1.
2.
3.
Thermochemical Equations
Is H negative or positive?
System absorbs heat
Endothermic
H > 0
H = 6.01 kJ
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6.3
Thermochemical Equations
Is H negative or positive?
System gives off heat
Exothermic
H < 0
H = -890.4 kJ
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6.3
H2O (l)
H = 6.01 kJ
H2O (s)
H =
- 6.01 kJ
2H2O (l)
H = 12.0 kJ
2 x 6.01kJ/mol
=12.0 KJ/2 mol
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When a reaction
is reversed, the
magnitude of H
remains the same,
but its sign
changes.
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H = 6.00 kJ
H2O(l)
H = 44.0 kJ
H2O(g)
266 g P4
P4O10 (s)
1 mol P4
123.9 g P4
-3013 kJ
1 mol P4
H = -3013 kJ
[ -6470 kJ]
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Enthalpy: Examples
4. The complete combustion of liquid octane, C8H18, to
produce carbon dioxide and liquid water at 25 C and
at constant pressure gives off 47.9 kJ per gram of
octane. Write a chemical equation to represent this
information.
[2C8H18(l) + 25 O2(g) 16 CO2(g) + 9H2O(l)
H = -1.09 x 104 kJ]
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Enthalpy: Examples
5.
6.
Enthalpy: Examples
7.
H = +52.96 KJ
8.
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Calorimetry
Calorimetry is
performed in
devices called
calorimeters
Calorimetry is
based on the
Law of
Conservation of
Energy
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Calorimetry
9. The specific heat of aluminum is 0.895 J/g C.
Calculate the heat necessary to raise the
temperature of 40.0 g of aluminum from -20.0
C to 32.3 C. Specific heat of aluminum is
0.215-cal/g C.
[1.87 x 103 Joules]
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Calorimetry:
Experimental measurement of heat produced in chemical and
physical processes
Heat Capacity, C, of a system:
the quantity of heat needed to raise the temperature of
matter 1 K.
Units: J/C
q
C
T
Molar Heat Capacity:
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heat capacity C
Specific heat
mass
m
Specific heat :
q
but C
T
C
q 1
q
cp
( )
m
T m
mT
q mc p T
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Calorimetry: Definitions
Heat (q) absorbed or released:
q = mcpt
q = Ct
t = tfinal - tinitial
When q>0 endothermic reaction
When q<0 exothermic reaction
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Calorimetry: Problems
12. What will be the final temperature if a 5.00-g
silver ring at 37.0 C gives off 25.0 J of heat to
the surroundings? Specific heat of silver = 0.235
J g-1 C-1
[15.7 C]
13. A 15.5 g sample of a metallic alloy is heated to
98.9 C and then dropped into 25.0 g of water in
a calorimeter. The temperature of the water
rises from 22.5 C to 25.7 C. Calculate the
specific heat of the alloy.
[0.29 J g-1 C-1]
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Calorimetry: Problems
14. Suppose a piece of gold with a mass
of 21.5 g at temperature of 95.00 C is
dropped into an insulated calorimeter
containing 125.0 g of water at 22.00 C.
What will be the final temperature of the
water?
[22.4 C]
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Bomb Calorimeter
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Uses Cp of water
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qwater = mwcpt
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Coffee-Cup Calorimeter:
Constant pressure
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Constant-Pressure Calorimetry
qsys = qwater + qcal + qrxn
qsys = 0
qrxn = - (qwater + qcalor)
qwater = mcpt
qcal = Ccalt
Reaction at Constant P
No heat enters or leaves!
Insulated system!
Pressure is constant.
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Calorimetry
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Calorimetry: Problem
17. A quantity of 1.00 x 102 mL of 0.500M HCl is
mixed with 1.00 x 102 mL of 0.500 M NaOH in a
constant pressure calorimeter having a heat
capacity of 335 J/ C. The initial temperature of the
HCl and NaOH solutions is the same, 22.50 C, and
the final temperature of the mixed solution is 24.90
C. Calculate the heat change for the neutralization
reaction and the molar heat of the neutralization
reaction. Assume s = 4.18 J/gC for the solution.
[-2.81 kJ; -56.2 kJ/mol]
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Chemistry in Action:
Fuel Values of Foods and Other Substances
C6H12O6 (s) + 6O2 (g)
1 cal = 4.184 J
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standard
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aA + bB
cC + dD
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H = -283.0 kJ
H = -393.5 kJ
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SO2 (g)
0
Hrxn
= -296.1 kJ
H0rxn = -1072 kJ
CS2 (l)
2. Add the given rxns so that the result is the desired rxn.
C(graphite) + O2 (g)
2S(rhombic) + 2O2 (g)
+ CO2(g) + 2SO2 (g)
C(graphite) + 2S(rhombic)
6.6
H0rxn = +1072 kJ
CS2 (l)
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Hrxn= -393.5 kJ
Hrxn = -285.8 kJ
Hrxn = -2598.8 kJ
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H solution= U + H hydration
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Heat of Dilution
The heat change associated with the
dilution of a solution.
Can be exothermic or endothermic
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