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Chapter Goals
8. Hess’s Law
9. Changes in Internal Energy, E
Energy
Capacity to do work
Units of energy:
. Joule; Kjoule (kJ)
. Calorie
. BTU (British Thermal Unit)
6.1
Energy Changes in Chemical Reactions
Heat is the transfer of thermal energy between two bodies that
are at different temperatures.
900C
400C
greater thermal energy
6.2
8 The First Law of
Thermodynamics
Exothermic
reactions
generate specific
amounts of heat.
This is because
the potential
energies of the
products are
lower than the
potential
energies of the
reactants.
10 The First Law of
Thermodynamics
This law can be stated as, “The combined amount of
energy in the universe is constant.”
The first law is also known as the Law of
Conservation of Energy.
Energy is neither created nor destroyed in chemical
reactions and physical changes.
11 Some Thermodynamic
Terms
The substances involved in the
chemical and physical changes
under investigation are called the
system.
In chemistry lab, the system is the
chemicals inside the beaker.
The environment around the system
is called the surroundings.
The surroundings are outside the
beaker.
The system plus the surroundings is
called the universe.
The system is the specific part of the universe that is of
interest in the study. SURROUNDINGS
SYSTEM
6.7
Changes
16 in Internal Energy, E
E 3.516 10 3 kJ
Changes in Internal Energy, E
E = E 2 - E1 = q + w
E = 1200 J + (-800 J)
E = 400 J
E sys = + 400 J
Changes
19 in Internal Energy, E
E surr 400 J
Changes in Internal Energy,
E
3. energy of the system in the new state, E2
E sys E 2 - E1
E 2 E1 E sys
E1 400 J
The First Law of
Thermodynamics
Exothermic reactions release energy in the form of heat.
For example, the combustion of propane is exothermic.
C 3 H 8 (g ) 5 O 2 (g ) 3 C O 2 (g ) 4H 2 O ( ) 2.22 10 3 kJ
The combustion of n-butane is also exothermic.
2 C 4 H 1 0 (g ) 13 O 2(g ) 8 C O 2 (g ) 10 H 2 O ( ) 5.78 10 3 kJ
Enthalpy (H) is used to quantify the heat flow into or out of a
system in a process that occurs at constant pressure.
H = H (products) – H (reactants)
H = heat given off or absorbed during a reaction at constant pressure
Is H negative or positive?
Endothermic
H > 0
Is H negative or positive?
Exothermic
H < 0
6.3
Thermochemical Equations
1 mol P4 3013 kJ
266 g P4 x x = 6470 kJ
123.9 g P4 1 mol P4
6.3
The specific heat (s) of a substance is the amount of heat (q)
required to raise the temperature of one gram of the
substance by one degree Celsius.
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.
C = ms
6.4
How much heat is given off when an 869 g iron bar cools
from 940C to 50C?
s of Fe = 0.444 J/g • 0C
6.4
Constant-Volume Calorimetry
Reaction at Constant V
H = qrxn
H ~ qrxn
No heat enters or leaves!
6.4
Constant-Pressure Calorimetry –
A coffee-cup calorimeter
is used to measure the amount of heat produced
(or absorbed)
in a reaction at constant P
qsys = qmix + qcal + qrxn
qsys = 0
qrxn = - (qmix + qcal)
qmix = mst
qcal = Ccalt
Reaction at Constant P
H = qrxn
q P mCT
.
= 50.00 g 4184 J 0
g C 12.54 C
0
262337
. J 2623 J
33 Calorimetry
3.425 kJ = 3425 J
3425 J - 2623 J = 802 J
4. Find the heat capacity of the calorimeter.
(heat absorbed by the calorimeter)/(temperature change)
802 J
0
63.955 J
0
C
64.00 J
0
C
12.54 C
34 Calorimetry
CH3COOH(aq) + NaOH(aq)
NaCH3COO(aq) + H2O()
When we add 25.00 mL of 0.500 M NaOH at
23.000oC to 25.00 mL of 0.600 M CH3COOH already
in the calorimeter at the same temperature, the
resulting temperature is observed to be 25.947oC.
35 Calorimetry
temperature
temperature
temperature change
change
change
=
T = 25.947 - 23.000
T 25.947 - 00 0 C = 2.947
23.000 C
23.000 0
2.947 CC C
C == 2.947 00
heatabsorbed
heat absorbed
byby calorimeter
calorimeter
q =
q = 2.947
2.9470 C 27.8
0
J
0
J
C 27.8 C 819
0 819
. J
C
. J
mass of solution in calorimeter
1.02 g
25.00 mL + 25.00 mL 510
. g
mL
37 Calorimetry
q = 51.0 g 418
. J
g0 C
2.947 0 C 628 J
total amount of heat produced by reaction
q = 81.9 J + 628 J = 709.9 J
Calorimetry
38
aqaq NaCH
CH 3COOH NaCH 3COO
aq + aq
NaOH 3COO aq2 +
CH 3COOH + NaOH aq + H O l H 2 O
l
0.500 mmol NaOH
25.00 mL NaOH 0.500 mmol NaOH
mL NaOH 1 mL NaOH
25.00
1 mL NaOH
1 mmol NaCH 3COO 12.5 mmol NaCH COO
1 mmol
NaCH
1 mmol COO
NaOH 3
3
12.5 mmol NaCH 3COO
1 mmol NaOH 0.600 mmol CH 3COOH
25.00 mL CH 3COOH
1 mL CH 3COOH
1 mmol NaCH 3COO
15.0 mmol NaCH 3COO
1 mmol CH 3COOH
Calorimetry
39
Mg s Cl 2 g MgCl 2 s 6418
. kJ
o
H f MgCl 2 s 6418
. kJ / mol
Standard Molar Enthalpies of
Formation, Hfo
Standard molar enthalpies of formation have been
determined for many substances and are tabulated in
Table 15-1 and Appendix K in the text.
Standard molar enthalpies of elements in their most
stable forms at 298.15 K and 1.000 atm are zero.
Example 15-4: The standard molar enthalpy of formation for
phosphoric acid is -1281 kJ/mol. Write the equation for the
reaction for whichHorxn = -1281 kJ.
P in standard state is P4
Phosphoric acid in standard state is H3PO4(s)
You do it!
Standard Molar Enthalpies of
Formation, Hfo
3
2 H 2 g 2 O2 g 14 P4 s H3PO 4 s 1281 kJ
o
Hf H3PO4 s 1281 kJ / mol
45
Standard Molar Enthalpies of
Formation, Hfo
Example 15-5: Calculate the enthalpy
change for the reaction of one mole of H2(g)
with one mole of F2(g) to form two moles of
HF(g) at 25oC and one atmosphere.
H 2 g F2 g 2 H F g
std. state std. state std. state
for this rxn. H o298 2 H of
from A ppen dix K , H of 271 kJ / m ol
H o298 2 m ol 271 kJ / m ol 542 kJ
The standard enthalpy of reaction (Hrxn
0
) is the enthalpy of
a reaction carried out at 1 atm.
aA + bB cC + dD
Hrxn
0
= [ cH0f (C) + dH0f (D) ] - [ aH0f (A) + bH0f (B) ]
Hrxn
0
= nH0f (products) - mHf0 (reactants)
Benzene (C6H6) burns in air to produce carbon dioxide and
liquid water. How much heat is released per mole of
benzene combusted? The standard enthalpy of formation
of benzene is 49.04 kJ/mol.
2C6H6 (l) + 15O2 (g) 12CO2 (g) + 6H2O (l)
Hrxn
0
= nH0f (products) - mHf0 (reactants)
Hrxn
0
= [ 12H0f (CO2) + 6H0f (H2O)] - [ 2Hf0 (C6H6) ]
Hrxn
0
= [ 12x–393.5 + 6x–285.8 ] – [ 2x49.04 ] = -6,534.88 k
-6534.88 kJ
= - 3267.44 kJ/mol C6H6
2 mol
6.5
Hess’s Law
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.
N 2 O g + N O 2 g 3 NO g H o ?
You do it!
Hess’s
53 Law