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THERMOCHEMISTRY
FOUNDATION CHEMISTRY I
CHM092 2015
Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
Topic
CHAPTER 5
5.1
5.2
5.3
5.4
5.5
5.6
5.7
Introduction to Thermochemistry
System and Surroundings
Exothermic and Endothermic Reactions
Enthalpy, H
Specific Heat Capacity and Calorimetry
Standard Enthalpy
Enthalpy Changes of Chemical Reactions
Direct method and indirect method: Hesss Law
5.8
Topic
5.1 Introduction to
Thermochemistry
Thermometer
Checkpoint 1
Name two ways can an object possess energy?
How do these two ways differ form one another?
Topic
5.2 System and
Surroundings
Surroundings
Surroundings
System
System
=0
Example:
C3H8 + 5O2
3CO2 + 4H2O
Exothermic chemical reaction!
Chemical energy lost by combustion = Energy gained by the surroundings
system
surroundings
Esurroundings is +ve
Therefore:
Esystem= Esurroundings
Surroundings
DE +
System
DE
Esurroundings is ve
Therefore:
Esystem= Esurroundings
Surroundings
DE
System
DE +
Open systems both matter (mass) and energy can move into and
5.2 System and Surroundings
out of an open system. The earth, for example, is an open system.
Types
ofand
System
Energy comes in from
the sun,
is re-radiated back to space.
Meteors strike the Earth, and cause parts of the Earth to be
Open systems
cansend
exchange
and energy,
usually
ejected
into space.We
satellitesmass
into interstellar
space.
Thesein
formtoofstudy
heatscientifically
with its surroundings.
are difficultthe
systems
because there are too
many variables to track.
Closed systems matter cant be transferred from a closed
system, but energy can. We study these frequently, and a great
example is the ubiquitous coffee cup calorimeter used in many
general chemistry laboratories. These are great ways to see how a
system (some chemical reaction) causes a change in temperature
in the surroundings (the solvent, often water) that is contained in
the cup.
Isolated systems neither matter or energy can be transferred
The
anan
open
system.
Energy
comes
in
The earth,
earth,for
forexample,
example,isis
open
system.
Energy
comes
from in
thefrom
sun,the
andsun,
is re-radiated
back to space.
and is re-radiated
back to space.
from these systems to the surroundings
Internal Energy
Ereaction = Esurroundings
System
CO
O22
C
+ 2OC
2 +CO
E = q + 0 = q
The two cases where energy is transferred as heat only.
1. Heat flowing out from a system.
2. Heat flowing into a system
Zn(s) + 2H+(aq) +
2Cl-(aq)
H2(g) + Zn2+(aq) + 2Cl-(aq)
DU = q + w
The sum of the energy transferred as heat between the system and
surrounding (q)
The energy transferred as work between the system and its
surroundings (w)
U is represent the internal energy, but some textbook use E, doesnt
matter
23
Substance
DHcombustion (kJ/g)
Apple
-2
Beef
-8
Beer
-1.5
Gasoline
-34
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.
Topic
5.3 Exothermic and Endothermic
Reactions
27
DH = H (products) H (reactants)
ENDOTHERMIC
reactants
products
28
H2O (l)
Endothermic
DH > 0
H2O (s)
H2O (s)
H2O (l)
DH = 6.01 kJ/mol
29
CH4 + 2O2
DH < 0
CO2 + 2 H2O
Endothermic
Exothermic
32
Topic
5.4 Enthalpy
5.4 Enthalpy
Standard Enthalpy/ Heat of Reaction, H
Enthalpy (H) is the amount of heat energy measured at
constant pressure of a chemical reaction.
Standard enthalpy change/heat of reaction, H, is the
enthalpy change when all reactants and products are in
their standard states
The standard state is the state of a material at a defined
set of conditions
pure gas at exactly 1 atm pressure
pure solid or liquid in its most stable form at exactly 1
atm pressure and temperature of interest usually 25 C
substance in a solution with concentration 1M
5.4 Enthalpy
Standard Enthalpy/ Heat of Reaction, H
There are 3 basic rules to apply when we use
thermochemical equations for calculation.
i.
5.4 Enthalpy
Standard Enthalpy/ Heat of Reaction, H
ii. If any of the equations above are reversed, the enthalpy
change, H, will have the same numerical value but with
an opposite sign. That is, the reverse of an endothermic
reaction is exothermic and vice versa.
DH = 6.01 kJ/mol
H2O (l)
H2O (s)
DH = -6.01 kJ/mol
2H2O (l)
DH = 2 x 6.01 = 12.0 kJ
38
H2O (l)
DH = 6.01 kJ/mol
H2O (l)
H2O (g)
DH = 44.0 kJ/mol
39
Checkpoint 2
Topic
5.5 Specific Heat Capacity and
Calorimetry
q = C x T
The unit of temperature must be consistent either C or K.
The temperature difference is the measurement of the
relative amount of internal energy between two bodies.
5.5
5.5
q = m x s x T
heat capacity, C = m x s
q = C x DT
where DT= Tfinal - Tinitial
5.5
Checkpoint 3
Which substance in Table below will
undergo the greatest temperature
change when the same mass of each
substance absorbs the same quantity of
heat?
5.5
qhot = qcold
mhotCs,hotDThot = (mcoldCs,coldDTcold)
5.5
Example 5.2:
A 466-g sample of water is heated from 8.50C to 74.60C.
5.5
Example 5.2:
Strategy We know the quantity of water and the specific heat of water.
With this information and the temperature rise, we can calculate the amount
of heat absorbed (q).
Solution Using Equation (6.12), we write
Check The units g and C cancel, and we are left with the desired unit kJ.
Because heat is absorbed by the water from the surroundings, it has a
positive sign.
5.5
Example 5.3:
Checkpoint 4
How much heat (in kJ) is required to warm 2.5 kg of sand
from 25.0C to 100C
(specific heat of sand =0.84 J/g.C)
53
Checkpoint 5
The specific heat of ethylene glycol is 2.42 J/g.K. How
many of J of heat are needed to raise the temperature
of 62.0 g of ethylene glycol from 131.1C to 40.5C?
5.5
Constant-Volume Calorimetry:
Bomb Calorimeter
Calorimetry is the measurement of
heat changes.
Constant-volume calorimetry
Isolated system
Measures DU
Typical procedure used in a bomb
calorimeter.
Known amount of sample placed in steel
container and then filled with oxygen gas.
Steel chamber submerged in known
amount of water.
Sample ignited electrically.
Temperature increase of water is
determined.
5.5
Constant-Volume Calorimetry:
Bomb Calorimeter
qsys = qwater + qbomb + qrxn
qsys = 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!
56
5.5
Example 5.4:
5.5
Example 5.3:
Strategy
Knowing the heat capacity and the temperature rise, how do we calculate
the heat absorbed by the calorimeter?
Because qsys = qcal + qrxn = 0, qcal = qrxn. The heat change of the reaction is
57.66 kJ. This is the heat released by the combustion of 1.435 g of C10H8;
therefore, we can write the conversion factor as
5.5
Example 5.3:
Check Knowing that the combustion reaction is exothermic and that the
molar mass of naphthalene is much greater than 1.4 g, is the answer
reasonable? Under the reaction conditions, can the heat change (257.66 kJ)
be equated to the enthalpy change of the reaction?
Checkpoint 6
A quantity of 1.922 g of methanol (CH3OH) was
burned in a constant-volume bomb calorimeter.
Consequently, the temperature of the water rose by
4.20C. If the quantity of water surrounding the
calorimeter was 2000g and the heat capacity of the
calorimeter was 2.02 kJ/C, calculate the molar heat
combustion of methanol.
61
PLAN:
- q sample = qcalorimeter
SOLUTION: qcalorimeter
40.24 kJ
= heat capacity x DT
= 8.151 kJ/K x 4.937 K
= 40.24 kJ
kcal
4.184 kJ
The manufacturers claim is true.
5.5
Constant-Pressure Calorimetry
System: reactants and products
Surroundings: water
Used to measure:
Specific heats
DH values
qsys = qwater + qcal + qrxn
qsys = 0
qrxn = - (qwater + qcal)
qwater = m x s x Dt
qcal = Ccal x Dt
Reaction at Constant P
DH = qrxn
5.5
Example 5.5:
A lead (Pb) pellet having a mass of
26.47 g at 89.98C was placed in a
constant-pressure calorimeter of
negligible heat capacity containing
100.0 mL of water.
The water temperature rose from
22.50C to 23.17C.
What is the specific heat of the lead
pellet?
5.5
Example 5.5:
Strategy A sketch of the initial and final situation is as follows:
We know the masses of water and the lead pellet as well as the initial and
final temperatures. Assuming no heat is lost to the surroundings, we can
equate the heat lost by the lead pellet to the heat gained by the water.
Knowing the specific heat of water, we can then calculate the specific heat of
lead.
5.5
Example 5.5:
Solution Treating the calorimeter as an isolated system (no heat lost to the
surroundings), we write
or
5.5
Example 5.5:
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
68
Checkpoint 7
A quantity of 1.00 x 102 mL of 0.500 M HCl is mixed with
1.0 x 102 mL of 0.50 M Ba(OH)2 in a constant-pressure
calorimeter having a heat capacity of 335 J/C. The initial
temperature of both solutions is the same at 22.50C. The
final temperature of the solution is 24.90C. Calculate the
heat change for the neutralization reaction.
NaOH (aq) + HCl (aq) NaCl (aq) + H2O (l)
Assume that the densities and specific heats of the solutions are the
same as for water (1.00 g/mL and 4.184 J/C, respectively)
69
Topic
5.6 Standard Enthalpy
DH0f (O2) = 0
DH0
72
= -1207 kJ mol-1
Checkpoint 8
a) Write a thermochemical equation for the formation of
ethanol, C2H5OH (l) under standard conditions. The Hf of
C2H5OH (l) = -287 kJ/mol
b) Write the formation reactions for C7H12O(l) and Al2(SO4)3 (S)
O2 (g)
H2O (l)
D oc = -286 kJ
Given:
Find:
Conceptual
Plan:
Relationships:
q, kJ/mol
kg
mol
kJ
Solution:
Check:
q, kJ/mol
Find:
Concept Plan:
Relationships:
mol
kJ
Solution:
Check:
Checkpoint 9
According to thermochemical equation for the combustion
of acetone:
C H O(l) 4O (g) 3CO (g) 3H O(g)
3 6
2
2
2
Ho 1790kJ
81
Ho = 57.3 kJ
mol1
mol1
H = 57.3 kJ mol1
Ho = 69.0 kJ mol1
85
Topic
5.7 Enthalpy Changes of
Chemical Reactions
DIRECT METHOD
Hreaction= nHf(products) nHf(reactants)
INDIRECT METHOD
HESSS LAW
aA + bB
cC + dD
DH0rxn = [cDH0f (C) + dDH0f (D) ] - [ aDH0f (A) + bDH0f (B) ]
DH0rxn = S nDH0f (products) - S nDH0f (reactants)
Where means sum and n is the coefficient of the reaction
Figure 6.12
Elements
-DHof
formation
Reactants
decomposition
Enthalpy, H
DHof
Hinitial
DHorxn
Products
Hfinal
DHorxn = S nDHof(products) - S nDHof(reactants)
Checkpoint 10
Calculate the DH
rxn for decomposing 10.0 g of
limestone, CaCO3, under standard conditions.
CaCO3(s) CaO(s) + O2(g)
Given:
Solution
- H for the forming CO (g) from C (graphite) and O2 (g) can be
determined indirectly, as long as H for other reactions is
already measured.
DH = 2(227.4) kJ
DH = 4(393.5) kJ
DH = 2(285.8) kJ
DH = 2600.4 kJ
Checkpoint 11
Use Hesss Law to calculate the standard enthalpy of formation
of acetylene (C2H2) from its elements:
Topic
5.8 Lattice Energy & Born-Haber
Cycle
Lattice Energy
The extra stability that accompanies the formation
of the crystal lattice is measured as the lattice
energy
The lattice energy is the energy released when
the solid crystal forms from separate ions in the
gas state under standard condition.
Provide a measure of strength of ionic bond between
ions in the crystal lattice.
always exothermic
hard to measure directly, but can be calculated from
knowledge of other processes
NaCl (s)
H = -770 kJ
H (g)
Na(g)
H = +216 kJ
H = +109 kJ
H2 (g)
2H (g)
H = +432 kJ mol-1
H=
155.2
Li(g)
Consider Li
the(s)
reaction
between
lithium
andkJ
fluorine
1
F2 (g) F (g)
H=
75.3 kJ
2
109
H=
520 kJ
3
H=
-328kJ
4
H=
?
5
H=
155.2 kJ
1
F2 (g) F (g)
H=
75.3 kJ
2
Li (g) Li+(g) + e-
H=
520 kJ
3
F(g) + e- F-(g)
H=
4 -328kJ
f (s) H= ?
Li+(g) + F-(g) LiF
5
overall
= -594.1 kJ
111
Na(s)
+ 121
+ 500
364
Hoverall
+ 108
?
411
= H
1 + H
5
3 + H
2 + H
4 + H
H=
?
5
Na+(g) + Cl(g)
Na(s)
3
NaCl(s)
>
Na(g)
Cl2(g) >
Na+(g) + Cl(g)
Cl(g)
Na(g) + Cl(g)
Cl(g) + e
6
>
3
Na(g) + Cl2(g)
Cl(g)
2
Na(s) + Cl2(g)
1
NaCl(s)
Na+(g) + Cl(g)
5=
-4
-3
-2
-1
5
6
1
Na(s) Na(g)
Cl2(g) Cl(g)
Na(g) Na+(g)
Cl (g) Cl(g)
Na+ (g) + Cl(g) NaCl(s)
lattice)
Na(s) + Cl2(g) NaCl(s)
Na+(g) + Cl(g)
Na(g) + Cl(g)
+108 kJ
+(121 kJ)
+500kJ Na(s)
364 kJ
DH (NaCl
411 kJ
Na(g) + Cl2(g)
+ Cl2(g)
1
NaCl(s)
Na+(g) + Cl(g)
OR
4
Na+(g) + Cl(g)
Na(g) + Cl(g)
-1 3
Na(g) + Cl2(g)
Na(s) + Cl2(g)
1
NaCl(s)
Answer
DHlattice energy = -2522 kJ/mol
End of Chapter 5