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THERMODYNAMICS
[LEARNING OBJECTIVES
§ Recall basic concepts and terminologies in
thermodynamics such as
üHeat and Temperature
üHeat capacity, molar heat capacity, specific heat
capacity
üOpen system, closed system, isolated system,
üEndothermic and exothermic,
üSpontaneity of Reactions
üInternal energy, enthalpy, entropy,
üCalorimetry
üHess’s Law
[THERMODYNAMICS
Study of energy and
its inter-conversion
[ENERGY
q Capacity to do work
[ENERGY
q Capacity to do work
[FORMS OF ENERGY
q Radiant Energy
- comes from the sun and
is earth’s primary
energy source
[FORMS OF ENERGY
H2O
CO2
O2
C6H12O6
[FORMS OF ENERGY
q Chemical Energy
- Energy stored within the bonds of chemical
substances
H2O
CO2
O2
C6H12O6
[FORMS OF ENERGY
q Chemical Energy
- Energy stored within the bonds of chemical
substances
H2O
CO2
O2
C6H12O6
[FORMS OF ENERGY
q Thermal Energy
- Energy associated with the random motion of
atoms and molecules
[FORMS OF ENERGY
q Potential Energy
- Energy available
by virtue of an
object’s position
[FORMS OF ENERGY
q Nuclear Energy
- Energy stored within the collection of
neutrons and protons in the atom
[FORMS OF ENERGY
[
LAW OF CONSERVATION OF ENERGY
[
LAW OF CONSERVATION OF ENERGY
[ENERGY UNITS
q Heat energy is often measured in calories, cal, or
Joules, J, (kg-m2/s2)
UNIVERSE
System
= object of study
Surrounding
= region outside the system
Boundary
= separating interface
OPEN SYSTEM
CLOSED SYSTEM
ISOLATED SYSTEM
OPEN SYSTEM
CLOSED SYSTEM
ISOLATED SYSTEM
OPEN CLOSED ISOLATED
Movable piston
GAS Expansion of gas
- Piston is pushed upwards
- Gas does work
Work Done by the System
w = F x d
DV > 0
w = -PoppDV
-PoppDV < 0
F wsys < 0
P x V = x d3 = F x d = w
d2
initial final
[ INTERNAL ENERGY
INTERNAL ENERGY, U
§ total energy of a system
§ Total kinetic energy (KE) and potential energy (PE) of the
particles in the system
CONTRIBUTIONS TO U OF A SUBSTANCE
§ KE of the motion of individual particles
§ PE that arises from interactions between particles
§ KE and PE of nuclei and electrons within the
individual particles
Absolute value of U cannot be measured
Only ΔU can be measured
[THERMODYNAMICS
- Involves the study of the changes in the state of the
system
DU = Ufinal - Uinitial
DP = Pfinal - Pinitial
DV = Vfinal - Vinitial
DT = Tfinal - Tinitial
Potential energy of hiker 1 and hiker
2 is the same even though they took
different paths.
[ FIRST LAW OF THERMODYNAMICS
“ The internal energy of an isolated system is constant”
DUsystem + DUsurroundings = 0
Closed system
DUsystem = -DUsurroundings Change in U (∆U) is equal
to the E that passes
through a boundary as
Isolated system heat (q) or work (W)
constant U (∆U =0)
q = 0; W = 0
∆U = q + W
[
FIRST LAW OF THERMODYNAMICS
∆U = q + W
∆U (+) INCREASE in internal E of system
∆U (-) DECREASE in internal E of system
q (+) heat ABSORBED by the system from
surrounding (ENDOTHERMIC)
q (-) heat RELEASED by the system from
surrounding (EXOTHERMIC)
W (+) work done ON the system by the
surrounding
W (-) work done BY the system on the
surrounding
[
FIRST LAW OF THERMODYNAMICS
∆U = q + W
∆U = q ∆U = W
No work done No heat transferred
Work IN
Work OUT
∆𝑈 = +515𝐽 + −218𝐽 = 297𝐽
Q = (+) because heat is added
W = (-) because the gas (system) does the work
Sample problem 1
101.3 𝐽 = 1 𝐿 2 𝑎𝑡𝑚
[Calorimetry
is the measurement of state variables for the purpose
of deriving the heat transfer associated with changes
of its state due for example to :
• Chemical reactions
• Physical changes/
Phase transitions
The heat capacity (C) of a substance is the amount of heat
(q) required to raise the temperature of a given quantity
(m) of the substance by one degree Celsius.
𝑞 = 𝑚 𝑥 𝑠 𝑥 ∆𝑇
𝑞 = 466 𝑔 4.184𝐽/𝑔 2> 𝐶 74.60> 𝐶 − 8.50> 𝐶
𝑞 = 128878 𝐽 ≈ 129 𝑘𝐽
Learning Check
A 26.2 g piece of copper metal is heated from
21.5°C to 201.6°C. Calculate the amount of
heat absorbed by the metal. The specific heat
of Cu is 0.385 J/g·°C
Answer: 1816.67 J
Learning Check
The heat capacity of 5 grams of gold is
0.645 J/°C.
a) What is the specific heat of gold?
b) What is the molar heat capacity of
gold? Molar mass of gold is 196.97
g/mol
Answers:
a. 0.129 J/goC
b. 25.4 J/moloC
Learning Check
Answer: 28.96oC
51
SEATWORK (1/4 yellow sheet)
1. Aluminum metal has a specific heat of 0.900
J/g·°C. Calculate the amount of heat required
to raise the temperature of 10.5 moles of Al
from 30.5 °C to 225°C
2. A piece of copper with a mass of 218 g has a
heat capacity of 83.9 J/°C. What is the
specific heat of copper?
HOMEWORK (1/4 yellow sheet)
1. Three separate 3.5g blocks of Al, Cu, and Fe
at the same temperature each absorb same
amount of heat. Which block reaches the
highest temperature? The specific heats of
Al, Cu and Fe are 0.900 J/g·°C, 0.385 J/g·°C,
and 0.444 J/g·°C, respectively.
2. A 12 moles sample of H2O at 85°C is cooled.
The water loses a total of 15 kJ of energy in
the cooling process. What is the final
temperature of the water? The specific heat
of water is 4.184 J/g·°C
[LEARNING OBJECTIVES
q Describe how changes in enthalpy and
thermal energy accompanying a chemical
reaction can be measured calorimetrically.
q Solve problems involving determination of
specific heat, heat capacity, heat loss or heat
gained by system and enthalpy of reaction
using calorimetry.
q Interpret thermochemical equations for
combustion and formation reactions.
[LEARNING OBJECTIVES
q Use thermochemical equations and
stoichiometry to determine amount of heat
lost or gained in a chemical reaction
q Calculate the molar enthalpy of dissolution
from calorimeter experimental data.
[USEFUL EQUATIONS
q = m x s x DT C = m x s
q = C x DT C = Cm x mol
DT = Tfinal - Tinitial Cm = MM x s
Constant-Volume Calorimetry
qsys + qsurr = 0
qsys = qrxn
qsurr = qwater + qbomb
qrxn + qwater + qbomb = 0
qrxn = - (qwater + qbomb)
qwater = m x s x DT
qbomb = Cbomb x DT
Reaction at Constant V
DH ≠ qrxn
DH ~ qrxn
No heat enters or leaves!
Sample Problem
A quantity of 1.435 g of naphthalene
(C10H8) , a pungent-smelling substance
used in moth repellents, was burned in
a constant-volume bomb calorimeter.
qsys + qsurr = 0
qsys = qrxn
qsurr = qwater + qcal
qrxn + qwater + qcal = 0
qrxn = - (qwater + qcal)
qwater = m x s x DT
qcal = Ccal x DT
Reaction at Constant P
DH = qrxn
OR
𝑞CDE = 𝑚𝑠∆𝑇
where m and s are the mass and specific heat and
DT = Tfinal − Tinitial
Therefore,
Because the heat lost by the lead pellet is equal to the heat
gained by the water, qPb = −280.3 J. Solving for the specific
heat of Pb, we write
𝑞FG = 𝑚𝑠∆𝑇
65
Sample Problem
A quantity of 100.0 mL of 0.500 M HCl was mixed with 100.0
mL of 0.500 M NaOH in a constant-pressure calorimeter of
negligible heat capacity. The initial temperature of the HCl
and NaOH solutions was the same, 22.50°C, and the final
temperature of the mixed solution was 25.86°C. Calculate the
heat change for the neutralization reaction:
DU = q + w
q = 0
w < 0, DU < 0
DU = CDT
DT < 0, SNOW!
Enthalpy and the First Law of Thermodynamics
DU = q + w
At constant pressure:
q = DH and w = -PDV
DU = DH - PDV Relationship of
DH = DU + PDV DH and DU
71
Exothermic process is any process that gives off heat – transfers
thermal energy from the system to the surroundings.
2H2 (g) + O2 (g) 2H2O (l) + energy
73
Enthalpy (H) is used to quantify the heat flow into or out of
a system in a process that occurs at constant pressure.
DH = H (products) – H (reactants)
DH = heat given off or absorbed during a reaction at constant pressure
Is DH negative or positive?
Endothermic
DH > 0
Is DH negative or positive?
Exothermic
DH < 0
CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (l) DH = -890.4 kJ/mol
Thermochemical Equations
82
6.4
Establish an arbitrary scale with the standard enthalpy of formation (DH0) as a reference
point for all enthalpy expressions.
f
Standard enthalpy of formation (DH0) is the heat change that results when one mole
f
of a compound is formed from its elements at a pressure of 1 atm.
The standard enthalpy of formation of any element in its most stable form is zero.
89
Which of the following has a DH°f = 0 kJ/mol?
A) NO(g)
B) CS2(l)
C) Fe2+(aq)
D) H2O(l)
E) N2(g)
Answer: E
N2(g) is the most stable
form for Nitrogen.
90
The standard enthalpy of reaction(DH0rxn) is the enthalpy of a
reaction carried out at 1 atm.
aA + bB cC + dD
91
The thermite reaction involves
aluminum and iron(III) oxide
Given that
ΔH°f[CO2(g)] = –393.5 kJ/mol
ΔH°f[H2O(l)] = –285.8 kJ/mol
Calculate the standard enthalpy of formation of octane.
Hess’s Law: When reactants are converted to products, the
change in enthalpy is the same whether the reaction takes
place in one step or in a series of steps.
106
The Solution Process for NaCl
SPONTANEOUS NON-SPONTANEOUS
ΔG = ΔH -T ΔS
ΔG = (-) SPONTANEOUS
ΔG = (+) NON-SPONTANEOUS
ΔH = enthalpy change
T = temperature in Kelvin
ΔS = entropy change
[ENTROPY, S