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THERMODYNAMICS
[LEARNING OBJECTIVES
▪ Recall basic concepts and terminologies in
thermodynamics such as
✓Heat and Temperature
✓Heat capacity, molar heat capacity, specific heat
capacity
✓Open system, closed system, isolated system,
✓Endothermic and exothermic,
✓Spontaneity of Reactions
✓Internal energy, enthalpy, entropy,
✓Calorimetry
✓Hess’s Law
[THERMODYNAMICS
Study of energy and
its inter-conversion
[ENERGY
❑ Capacity to do work
[ENERGY
❑ Capacity to do work
[FORMS OF ENERGY
❑ Radiant Energy
- comes from the sun and
is earth’s primary
energy source
[FORMS OF ENERGY
H2O
CO2
O2
C6H12O6
[FORMS OF ENERGY
❑ Chemical Energy
- Energy stored within the bonds of chemical
substances
H 2O
CO2
O2
C6H12O6
[FORMS OF ENERGY
❑ Chemical Energy
- Energy stored within the bonds of chemical
substances
H 2O
CO2
O2
C6H12O6
[FORMS OF ENERGY
❑ Thermal Energy
- Energy associated with the random motion of
atoms and molecules
[FORMS OF ENERGY
❑ Potential Energy
- Energy available
by virtue of an
object’s position
[FORMS OF ENERGY
❑ 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
❑ 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
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
[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 ∙𝑜 𝐶 74.60𝑜 𝐶 − 8.50𝑜 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
[LEARNING OBJECTIVES
❑ Describe how changes in enthalpy and
thermal energy accompanying a chemical
reaction can be measured calorimetrically.
❑ Solve problems involving determination of
specific heat, heat capacity, heat loss or heat
gained by system and enthalpy of reaction
using calorimetry.
❑ Interpret thermochemical equations for
combustion and formation reactions.
[LEARNING OBJECTIVES
❑ Use thermochemical equations and
stoichiometry to determine amount of heat
lost or gained in a chemical reaction
❑ Calculate the molar enthalpy of dissolution
from calorimeter experimental data.
[USEFUL EQUATIONS
q = m x s x DT C=mxs
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
𝑞𝐻2𝑂 = 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
𝑞𝑃𝑏 = 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:
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
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.
SPONTANEOUS NON-SPONTANEOUS
ΔG = ΔH -T ΔS
ΔG = (-) SPONTANEOUS
ΔG = (+) NON-SPONTANEOUS
ΔH = enthalpy change
T = temperature in Kelvin
ΔS = entropy change
[ENTROPY, S