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Module 6: Thermochemistry
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Introduction to Thermodynamics
Thermodynamics
- study of the interconversion of heat and other kinds of energy.
Thermodynamic state of a system defined by a set of condition that completely
specifies all the properties of the system, such as temperature, pressure, composition
(identity and amount) and physical state (gas, liquid, solid)
State Function depends only on the state of the system and not on the way in
which the came to be in that state (P,V, T)
- a change in a state function describes a difference between
two states. It is independent of the process or pathway by which the change
occurs.
X = Xfinal - Xinitial
The First Law of Thermodynamics
Statement:
1. Energy ca be converted from one form to another, but cannot be created or
destroyed.
2. The total energy of the isolated system is constant.
3. The sum of all energy changes for all system participating in a process must be zero.
Mathematical Statement:
Energy of the system + Energy of the surroundings = 0
Internal Energy (E) the total energy of the system due to potential and kinetic
energies.
E = Efinal - Einitial
Eststem + surroundings = o
Esystem = -Esurroundings
The change in internal energy, E, is determined by the heat flow, q, and the work, w
E = q + w
Sign Conventions for Work and Heat
Process
Work done by the system on the surroundings
Work done on the system by the surroundings
Heat absorbed by the system from the
surroundings
Heat absorbed by the surroundings from the
system
Sign
+
+
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Practice Exercise 6.2: The work done when a gas is compressed in a cylinder is 462J.
During the process, there is a heat transfer of 128J from the gas to the surroundings.
Calculate the energy change for this process.
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Module 6: Thermochemistry
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Work
In most chemical and physical changes, the only kind of work is pressure-volume work.
For gas expansion against a constant external pressure
P
P
V
gas
W = - PV
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Practice Exercise 6.3: A sample of gas expands by 22.4L against an average pressure of
2.5atm. How much work (kJ) is done in the process? Is the work done by the system or by
the surrounding?
PV = 0
E = qv
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Module 6: Thermochemistry
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Enthalphy of Reactions
For any reaction of the type
Reactants Products
H = H (products) H (reactants)
Thermochemical Equations
A thermochemical equation expresses the following:
1. Weight relationships
2. Physical states of reactant and products
3. Temperature
4. Pressure
5. Heat evolved or absorbed in the reaction
Characteristics of Hrxn
1. For any reaction, Hrxn = H (products) H (reactants)
2. It depends on the state of the substance
H2(g) + O2(g) H2O (l)
H = -285.8 kJ
H2(g) + O2(g) H2O (g)
H = -241.8 kJ
3. It is proportional to the amount of reactants and products
H2(g) + O2(g) H2O (l)
H = -285.8 kJ
2H2(g) +
O2(g) 2 H2O (l)
H = -571.6 kJ
4. It changes sign when a process is reverse
H2O (l) H2(g) + O2(g)
H = +285.8 kJ
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Practice Exercise 6.4: Calculate the heat involved when 74.6g of SO 2 (molar mass =
64.07g/mol) is converted to SO3.
Thermochemical reaction: SO2(g) + O2(g) SO3(g) H = -99.1kJ/mol
Calorimetry
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Module 6: Thermochemistry
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C = ms
q = mst
q = Ct
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Practice Exercise 6.5: A 466g sample of water is heated from 8.50 oC to 74.60oC.
Calculate the amount of heat absorbed (in kilojoules) by the water.
Calorimeter -
TYPES OF CALORIMETER
Constant-Volume Calorimetry used to determine the heat of combustion.
qcal + qrxn = 0
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Module 6: Thermochemistry
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qrxn = - qcal
qcal = Ccalt
where: Ccal = heat capacity of calorimeter
t = change in temperature
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Practice Exercise 6.6: When 0.7521 g of benzoic acid was burned in a calorimeter
Practice Exercise 6.7: A quantity of 1.00 x 102 mL of 0.5M HCl was mixed with 1.00 x 10 2
mL of 0.5M NaOH in a constant-pressure calorimeter of negligible heat capacity. The initial
temperature of the HCl and NaOH solutions was the same, 22.5 oC, and the final temperature
of the mixed solution was 25.86 oC. Calculate the heat change for the neutralization reaction
on a molar basis.
NaOH(aq) + HCl(aq) NaCl(aq) + H2O(l)
Assume that the densities and specific heats of the solutions are the same as for water
(1.00g/mL and 4.184J/g oC, respectively)
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Module 6: Thermochemistry
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Module 6: Thermochemistry
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Practice Exercise 6.10: Calculate the standard enthalpy change for the reaction
2 Al(s) + Fe2O3(s) 2 Fe(s) + Al2O3(s)
Given that
2 Al(s) + 3/2 O2(g) Al2O3(s)
Ho = -1669.8 kJ/mol
2Fe(s) +
3/2 O2(g)
Fe2O3(s)
Ho = - 822.2 kJ/mol
Solve Problems 6.15, 6.17, 6.25, 6.27, 6.33, 6.37, 6.51, 6.61, 6.63 ; pages 198 201
General Chemistry: The Essential Concepts, 5th edition by Raymond Chang
References:
General Chemistry: The Essential Concepts, 5th edition by Raymond Chang
Chemistry : 8th edition by Whitten, Davis, Peck and Stanley
CHEMISTRY: The Molecular Nature of Matter and Change , 4th ed. by Martin Silberberg
Chemistry: The General Science, 10th ed, by Brown, Le May and Bursten.
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Module 6: Thermochemistry
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Module 6: Thermochemistry
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