Title: Chapter 9 Energy, Enthalpy and Thermochemistry
1Chapter 9Energy, Enthalpy and Thermochemistry
- The study of energy and its interconversions is
called thermodynamics. - Kinetic Energy energy due to the motion of the
object (1/2 mv2) - Potential Energy energy due to position or
composition - Heat the transfer of energy between two objects
due to a temperature difference - Work a force acting over a distance
2Figure 9.1 (a) Initial position of balls
3Figure 9.1 (b) Final position of balls
4Energy of Matters
5State Function
- A property of the system depends only on its
present state. A state function does not depend
in any way on the systems past. - Energy is a state function, but work and heat are
not state function
6Combustion of methane
7Nitrogen/oxygen
8First Law of Thermodynamics
- The energy of the universe is constant
In closed system ?E ?Uqw (?????) q the
heat added to the system during the process w
the work done on the system during the
process qgt0 heat flows into the system from the
surroundings qlt0 an outflow of heat from the
system to the surroundings wgt0 work is done on
the system by the surroundings wlt0 the system
does work on the surroundings
9P-V Work
10P-V Work
11Enthalpy (?)
- The heat qp absorbed in a constant-pressure
- process equals the systems enthalpy change.
12- For a chemical reaction
- ?H?Hproducts-?Hreactants
- If ?Hreactantslt?Hproducts (endothermic)
- If ?Hreactantsgt?Hproducts (exothermic)
- Consider a constant-volume process
- dw-PdV0 (???????)
- ?Uqwqv
- ?Uqv
13Heat Capacity (???)
14Thermodynamics of Ideal Gases
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16Heat Capacity of Heating an Ideal Monatomic Gas
- Under constant volume, the energy flowing into
the gas is used to increase the translational
energy of the gas molecules.
17Heat Capacity of Ideal Monatomic Gases
Gas Cv (J/K mol) Cp (J/K mol)
He 12.47 20.8
Ne 12.47 20.8
Ar 12.47 20.8
18Heat Capacity of Diatomic Gases
Gas Cv (J/K mol) Cp (J/K mol)
H2 20.54 28.86
N2 20.71 29.03
19Heat Capacity of Polyatomic Gases
Gas Cv (J/K mol) Cp (J/K mol)
N2O 30.38 38.70
CO2 28.95 37.27
C2H6 44.60 52.92
20Heat Capacity of Heating a Polyatomic Gas
- Polyatomic gases have observed values for Cv that
are significantly greater than 3/2 R. - This larger value for Cv results because
polyatomic molecules absorb energy to excite
rotational and vibrational motions in addition to
translational motions.
21Cv and Cp of molecules
22Cv and Cp of Monatomic Gas
23Cv and Cp of H2O at 373K
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252 mol of monatomic ideal gas Calculate q, w, ?U
and ?H for both pathway
26- TA122K, TC366K, TB183K, TD61K
- Cv3/2R, Cp5/2R
- Path 1(A?C)
- w1-P?V-2atm(30-10)L101.3J/Latm-4.05103J
- q1qpnCp?T25/2(R)(366-122)1.01104J?H1
- ?U1nCv?T 23/2(R)(366-122)6.08103J
- Path 2(C?B)
- q2qvnCv?T23/2(R)(183-366)-4.56103J?U2
- ?H2nCp?T 25/2(R)(183-366)-7.6103J
- ?V0 w2 -P?V 0
27- Path 3(A?D)
- q3qvnCv?T23/2(R)(61-122)-1.52103J?U3
- ?H3nCp?T 25/2(R)(61-122)-2.53103J
- ?V0 w2 -P?V 0
- Path 4(D?B)
- w1-P?V-1atm(30-10)L101.3J/Latm-2.03103J
- q4qpnCp?T25/2(R)(183-61)5.08104J?H4
- ?U4nCv?T 23/2(R)(183-61)3.05103J
28Summary
- Path 1
- qpath1q1q25.5 103J
- wpath1w1w2 -4.05103J
- ?Hpath1 ?H1 ?H2 2.55103J
- ?Upath1 ?U1 ?U2 1.52103J
- Path 2
- qpath2q3q43.56103J
- wpath2w3w4 -2.03103J
- ?Hpath2 ?H3 ?H4 2.55103J
- ?Upath2 ?U3 ?U4 1.52103J
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30Calorimetry
- Specific heat capacity with unit JK-1g-1
- Molar heat capacity with unit JK-1mol-1
31Coffee Cup Calorimeter
- A constant-pressure calorimetry is used in
determining the change in enthalpy equals the
heat. - ?HqpnCp?T
32Bomb Calorimeter
332SO2(g)O2(g)?2SO3(g) ?H-198 KJ 2 mol. 1
mol. 2 mol. Calculate ?H and ?U
34- P is constant, ?Hqp-198 KJ (energy flow out of
system) - ?U qp w
- w-P?V and ?V?n(RT/P)
- T and P are constant, ?nnfinal-ninitial-1 mol
- So w-P?V-P?n (RT/P)
- - ?nRT-(-1)(8.314)(298)2.48 kJ
- ?U qp w-198 kJ2.48 kJ-196 kJ
35Hesss Law
- If a reaction is carried out in a series of
steps, ?H for the reaction will be equal to the
sum of the enthalpy changes for the individual
steps - The overall enthalpy change for the process is
independent of the number of steps or the
particular nature of the path by which the
reaction is carried out.
36- Consider the combustion reaction of methane to
- form CO2 and liquid H2O
- CH4(g) 2O2(g)? CO2(g) 2H2O(l)
- ?H1 -890KJ/mol
- This reaction can be thought of as occurring in
- two steps
- CH4(g) 2O2(g)? CO2(g) 2H2O(g)
- ?H2 -802 kJ/mol
- 2H2O(g)?2H2O(l)
- ?H3 -88KJ/mol
- ?H1 ?H2 ?H3
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38Standard Enthalpies of Formation
- The change in enthalpy that accompanies the
formation of 1 mole of a compound from its
elements with all substances in their standard
states. - The superscript zero indicates that the
corresponding process has been carried out under
standard conditions.
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42Present Sources of Energy
- Petroleum and Natural Gas Coal
New Energy Sources
Coal Conversion Hydrogen as a fuel
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46CO2 capture
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