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Energy Changes In Chemical Reactions
Learning Catalytics:
Chapter 6
Coverage:
6.2 The Nature of Energy: Key Definitions
6.3 The First Law of Thermodynamics: There is No Free Lunch
6.4 Quantifying Heat and Work
6.5 Measuring U for Chemical Reactions: Constant-Volume Calorimetry
6.6 Enthalpy: The Heat Evolved in a Chemical Reaction at Constant
Pressure
6.7 Constant-Pressure Calorimetry: Measuring rH
6.8 Relationships involving rH
6.9 Determining Enthalpies of Reaction from Standard Enthalpies of
Formation
Omitted
6.1 Chemical Hand Warmers
6.10 Energy Use and the Environment
2
Energy basics
Internal energy, heat, work and all that
Terminology
Thermochemistry: Study of changes in
-1648.4 kJ/mol
Units of Energy
SI: joule, J (nJ, J, mJ, kJ, MJ, GJ,)
Small j for joule, capital for symbol
Important: case of prefix matters (m = 10-3, M
= 106)
No period after symbol
Other units in common usage:
Calorie (cal) = 4.184 J
Big calorie (Cal) = 4,184 J (a kilocalorie, or
kcal)
Kilowatt-hour (kWh)
Questions
Does water at 20C possess energy? Explain.
What measurable value contains information
Energy
Internal energy (U): sum of energy of all
Questions
Which system has more energy, a litre of
ice)?
diffusion)
Heat/Work Analogy
Does your bank account contain the cash and
transferring value
BUT: Bank accounts do not contain cash or
cheques
What does a bank account contain? A balance.
work?
Heat & work are mechanisms for moving
energy
BUT: Chemical systems do not contain heat10or
11
Heat/Work Analogy
When money enters your bank account (by
12
Temperature question
The temperature of a system decreases
energy
It might have lost energy as heat or as work
13
>
>
<
<
0
0
0
0
;
;
;
;
w
w
w
w
>
<
>
<
0
0
0
0
;
;
;
;
U
U
U
U
>
=
=
<
0
0
0
0
14
Solution
During a reaction, some of the energy released by the
system is used to move a mass up a hill, while the air
temperature of the surroundings near the system
increases by 50 K. What are the relative values for q, w
and U, respectively?
ANS = D
Is w positive, negative, or zero?
Solution
A gas is contained in a piston-and-cylinder system,
oriented vertically. On top of the cylinder there is a
mass. When the gas is heated it expands, and the mass
is lifted. The energy used to lift the mass is exactly the
same as the energy absorbed from the heater. What are
the signs for q, w and U, respectively? ANS = B
Is q > 0, < 0, or = 0?
State functions
and path functions
18
20
Solution
Answer is C
Internal energy (U) is a state function
State functions have one value per state of the
system
Final state of A is same as final state of B
Therefore, A and B have same internal energy
22
path)
BUT: Uf and Ui do not depend on the path
23
24
10 g
water
25.00 C
100
J
hea
t
10 g Cu
25.00 C
10 g
water
27.39 C
=4.18Jg1C1
10 g Cu
50.97 C
Cs=0.385Jg1C1
25
substances
Allow calculation of temperature changes
E.g. How much heat is required to raise the
Heat exchange
Heat entering the system is equal and
Heat exchange
28
29
Pressure-Volume Work
30
Pressure-Volume Work
FinalState
InitialState
Pext
Pext
Vi
Pi>Pext
Gasexpands
againstPextuntil
pressuresequalise
Workdone:
w=Pext(VfVi)
Vf
Pf=Pext
31
Pressure-Volume Work
w = Fd
F is the force due to the external pressure
d is the distance the piston travels
w = (PextA)d
A is the cross-sectional area of the piston
w = Pext(Ad) = PextV
Sign convention: gas does work on surroundings when
it expands; therefore
w = -PextV
If Pext and P are in equilibrium during change
w = -P V
32
PV work example
11.7 L of gas in a cylinder-and-piston system
PV work example
Work: System and surroundings are in equilibrium so
w = -P V
Pa
w = - (1.03105 Pa)(24.1 11.7)10-3 m3 = - 1.28103
J
Heat is +1500 J so
Constant-Volume
Calorimetry
Measuring heats of reaction
35
Calorimetry
Purpose: measure
heat of combustion
V = 0 so w = 0
Process:
Burn substance
completely in
bomb
Carefully monitor
T of calorimeter
Calculate heat
transferred
36
Heat Capacity
First step: determine heat capacity of
calorimeter
Ccal = qcal/Tcal
Burn substance that gives off known amt of
heat
gained by calorimeter
37
Note on constant V
reactions
The energy change associated with a reaction
is denoted
rU
Since w = 0 when V = 0,
rU = q + w = qr,v
where the subscript v denotes constant volume
38
LC: Calorimetry
When 1.730 g of benzoic acid is burned in
oxygen in a calorimeter, the temperature of the
calorimeter increases by 2.95 K. If the heat
released from combustion of 1.000 g of benzoic
acid is 26.38 kJ, what is the heat capacity of the
calorimeter?
A. 13.0 kJ/K
B. 45.64 kJ/K
C. 15.5 kJ/K
D. 135 kJ/K
39
Answer
C. 15.5 kJ/K
Heat absorbed by the calorimeter is
qcal = (1.730 g)(26.38 kJ/g) = 45.64 kJ
And Tcal = 2.95 K
Ccal = qcal/Tcal
= (45.64 kJ)/(2.95 K)
= 15.5 kJ/K
15.5 kJ of heat required to raise temp by 1 K
40
LC: Calorimetry
A calorimeter (Ccal = 13.0 kJ/K) is used to measure
the energy of reaction for combustion of a
substance with molar mass 205.9 g/mol.
When 1.151 g of the substance is burned in O 2, the
temperature of the calorimeter increases by 1.62
K. What is the energy of reaction ( rU) in kJ/mol?
A. -0.118
B. -18.3
C. -1440
D. -3770
41
Answer
D. -3770 kJ/mol
qr = -Ccal Tcal = -(13.0 kJ/K)(1.62 K) = -21.06
kJ
It took 1.151 g to generate that much heat, so
qr,m = - 18.30 kJ/g
where the subscript m represents per unit
mass
= -3770 kJ/mol
42
Enthalpy
Our second energy state function
43
Enthalpy
Symbol: H
Change in enthalpy, H
Change in enthalpy on reaction, rH
Relationship to U
H = U + PV
Relationship to q
U = qv (heat for constant volume process)
H = qP (heat for constant pressure process)
Since chemical reactions are often performed at
45
Endothermic vs
Exothermic
Endothermic process:
H > 0
Heat is taken in from the surroundings
Exothermic process
H < 0
Heat is released to surroundings
46
Source of Confusion
Exothermic reactions release heat
Combustion is exothermic
Temp of combusting system rises as reaction
proceeds
If system releases heat, shouldnt temp
decrease?
47
Endothermic reaction
Ba(OH)2.8H2O(s) + 2 NH4SCN(s)
Ba(SCN)2(s) + 10 H2O(l)
+ 2 NH3(g)
48
Source of Confusion
Tables of H values for processes at 1 atm
and 298K
49
Endothermic example
Ba(OH)2(s)
NH4SCN(s)
q
25C
<25C
25C
Surr = 25C
Surr = 25C
Surr = 25C
H>0)
50
A-ha!
51
Another source of
confusion
The mol-1 in rH
e.g. 4 Fe(s) + 3 O2(g) 2 Fe2O3(s) rH = -1648.4 kJ/mol
per mole of what?
reaction
Otherwise, the per mole does not make sense
Oingo boingo!
53
Constant Pressure
Calorimetry
Constant V calorimetry yielded rU
recall: rU = qv
54
A crude calorimeter
Insulated
2 Styrofoam cups & cork cap
Loose cap
equilibrium with atmosphere
Thermometer & stirring rod
Measure temp changes for
Example
HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l)
50.0 mL of 1.00 M HCl are added to
56
Answer
The reaction takes place under constant P
Hrxn = -qH2O = -mH20Cs,H2OT
T = (27.5-21.0)C = 6.5C = 6.5 K
mH2O = H2OVH2O = (1.00 g/mL)(100 mL) = 100 g
Hrxn = -(100 g)(4.18 J/g/K)(6.5 K) = -2.7 kJ
Hrxn in molar units:
Moles HCl = (50.010-3 L)(1.00 mol/L) = 50.0103 mol
Hrxn = (-2.7 kJ)/(5010-3 mol) = -54 kJ/mol
57
Hesss Law
58
Hesss Law
If a reaction is carried out in a series of steps, rH is
the sum of all the rHs of the individual steps
Enthalpy arithmetic
If thermochemical equation multiplied by a
Example
What is the enthalpy of combustion of C 3H6 (g) if
C3H6(g) + H2(g) C3H8(g)
H = -124 kJ
Example
Rxn: C3H6 (g) + 9/2 O2 (g) 3 CO2 (g) + 3 H2O (l)
produces 1 fewer moles H2O than C3H8
& H2
62
Enthalpy Diagram
C3H6+H2 TotalReaction:
1
C
H
+H
+5O
3CO
+3H
O+
/2O2+H2
3
6
2
2
2
2
+5O2
Enthalpy
C3H8+5O2
NetReaction:
C3H6+9/2O23CO2+3H2O
3CO2+3H2O
+1/2O2+H2
3CO2+4H2O
63
Example
Formal steps in the reaction:
C3H6 (g) + H2 (g) C3H8 (g)
rH = -124 kJ
9
/
C3H8 (g) + 25O2 (g) 3 CO2 (g) 3+ 4 H2O (l) rH = -2220
kJ
H2O(l) 1/2 O2 (g) + H2(g)
rH = +286 kJ
C3H6 (g) + 9/2O2 (g) 3 CO2 (g) + 3 H2O (l) rH = -2058 kJ
Blue reaction reversed and divided by 2
rH for blue equn found by multiplying given rH by -1/2
64
Hint: start by writing out the full thermochemical equations (all three)
65
rH = +175.7
rH = -312.0
rH = -136.3
rH = rHethane - rHethylene
= -312.0 kJ/mol - (-175.3 kJ/mol)
= -136.3 kJ/mol (answer C)
67
68
Using fH to Calculate
rH
69
70
71
LC: rH
What is the standard enthalpy of reaction for
the photosynthesis of glucose:
6 CO2 (g) + 6 H2O (l) C6H12O6 (s) + 6 O2 (g)
fH
fH
fH
fH
72
Answer
rH = fH (glucose) + 6fH (O2)
- 6fH (CO2) 6fH (H2O)
= -1273 + 6(0) - 6(-393.5) - 6(-285.8)
= 2803 kJ/mol
73
74
Enthalpy Diagram
6H2O
6CO2
H=+23
61.
0kJ
Enthalpy
H=+
1714
.8kJ
6H2O+
6C+6O2
kJ
73
12
=
H
6H2+3O2+
6C+6O2
2
+
=
H
C6H12O6
+6O2
J
k
3
80
75
Summary
Energy
Internal energy, heat, and work
Heat capacity & heat transfer
P-V work
State functions vs path functions
Constant volume heat and energy changes
Enthalpy
Constant pressure calorimetry
Hesss Law
Enthalpy diagrams
Enthalpy of reaction & formation
76
Suggested Exercises
Review questions 1-29
Problems by topic 37, 39, 43, 45, 49, 53, 55,
57, 59, 63, 67, 71, 73, 75, 77, 79, 81, 83, 89,
117, 123, 133, 137, 139, 141
77