Professional Documents
Culture Documents
CHAPTER 6
Thermochemistry
1
Thermochemistry
• The study of the relationship between energy and chemistry
2
The Law of Conservation of Energy
Energy can be neither created nor destroyed. However, it
can be transferred from one object to another, and it can
assume different forms.
3
Definitions
• System
− The part of the universe we
chose to study
• Surroundings
− Everything with which the
system can exchange
energy
5
Internal Energy
ΔU = q + w
Where q is the heat transferred and w the work done.
6
Polling question
Consider a potato cannon which uses the ignition of a fuel to propel a potato a long
distance.
Consider the fuel and the molecules involved in combustion as the system.
If the burning of the fuel performs 800 J of work on the potato, and releases 1400 J
of energy as heat into the potato, what is ΔU of the fuel?
A) 2200 J
B) 600 J
C) -600 J
D) -2200 J
E) 0J
7
What is a State Function?
8
Internal energy vs. Heat / Work
H2(g) + ½ O2(g) → H2O(l)
9
Temperature Changes and Heat Capacity
• In the case of a material that does not change phase, the increase in temperature
of a system ΔT due to the input of a given amount of heat q is given by
• The heat capacity is a constant that depends on the mass and material of the
system
• Ex: one drop of water vs. a bucket of water
10
Temperature Changes and Heat Capacity
• Heat capacity is more useful when expressed
in terms of a given amount of a substance:
q = m Cs ΔT
11
Polling question
When 100 g of water at 50°C is brought into contact with 100 g of methanol at
0°C the final temperature of both substances is 40°C.
12
Sign convention and conservation of energy
qsystem = -qsurroundings
13
Let’s work a problem
A block of Cu has an initial temperature of 65.4°C. The Cu is immersed in a
beaker containing 95.7 g of H2O at 22.7°C. When the two substances reach
thermal equilibrium, the final temperature is 24.2°C. What is the mass of the Cu
block?
14
Work
• Often when a chemical reaction occurs, work is done in addition to heat transfer
(this is the principle of a car engine)
• Work is done when a force acts through a distance, many different “types” of
work possible
• In this course we will focus on pressure/volume (PV) work, only relevant for us
when gases are produced or consumed during a process
15
Pressure – Volume Work
16
Sign Convention - Pressure-Volume Work
• Similar sign conventions apply for work as for heat:
w is positive if work is done on the system by the surroundings (contraction of
gas, ΔV < 0)
w is negative if work is done by the system on the surroundings (expansion of
gas, ΔV > 0)
Example: If the air in a balloon expands from a volume of 0.100 L to 1.85 L against
a constant pressure of 1.00 bar, what is w with respect to the system?
17
Another way to calculate work
• Chemical reactions or other processes that produce or consume
gases result in work being performed
𝑤 = −𝑃Δ𝑉
18
Let’s work a problem
Formic acid (CH2O2) is a liquid that burns in oxygen to produce gaseous CO2 and
liquid H2O. Compute the pressure-volume work (per mole of formic acid) at 298 K.
1
𝐶𝐻2 𝑂2 𝑙 + 𝑂2 𝑔 → 𝐶𝑂2 𝑔 + 𝐻2 𝑂 𝑙
2
19
Measuring ΔrU for Chemical Reactions
Most widely used apparatus is the bomb calorimeter,
Operates at constant volume
X
20
Measuring ΔrU for Chemical Reactions
By measuring the heat transferred into the surroundings ΔrU can
be determined:
ΔU = qv + w
qr = ΔU
21
Polling question
If the bomb calorimeter shows an increase in temperature, which of the
following statements is correct?
A) The internal energy of the products is less than the internal energy of the
reactants
B) ∆U > 0
D) q + w = 0
Let’s work a problem
When 1.010 g of sucrose (C12H22O11) undergoes combustion in a bomb calorimeter,
the temperature rises from 24.922 °C to 28.331 °C. Find ΔrU for the combustion
(per mole of sucrose). The heat capacity of the bomb calorimeter is 4.901 kJ °C-1
23
Let’s keep one thing clear
• Internal energy change ΔrU always applies for the reaction, even if
not performed at constant volume
24
Enthalpy
Enthalpy (H) is the heat evolved in a chemical reaction at constant
pressure and is a state function:
H = U + PV
ΔH = ΔU + PΔV
ΔH = qp
25
Polling question
Determine DH and DU for the reaction and conditions depicted below.
You shouldn’t need a calculator, use logic!
26
Determination of ΔrH from Bomb Calorimetry Experiments
Using a bomb calorimeter we can also determine the
enthalpy of reaction by finding ΔrU and converting to
ΔrH using a simple formula
27
Let’s keep one thing clear
• Enthalpy change ΔrH always applies for the reaction, even if not
performed at constant pressure
• We then calculate ΔrH from ΔrU using the formula on previous slide
• The ΔrH value we calculated tells us what the heat of reaction would
be at constant pressure
28
Let’s work a problem
A 0.5224 g sample of C8H18 was combusted in a bomb calorimeter with a heat
capacity of 4.901 kJ °C-1. The temperature increased from 23.815 °C to 28.902 °C.
Determine ΔrH (per mole C8H18) for its complete combustion at 298 K.
Assume the products are gaseous CO2 and liquid H2O.
29
Exothermic and Endothermic Processes
ΔH is positive ΔH is negative
30
Constant-Pressure Calorimetry: Measuring ΔrH
• Coffee cup provides an insulated container for a
reaction to take place at constant pressure
31
Let’s work a problem
The following reaction is conducted in a coffee-cup calorimeter
0.158 g of Mg was reacted with excess HCl in water with a total volume of 100.0
mL. The temperature of the water rose from 25.6°C to 32.8°C. The Cs for water is
4.184 J g-1 °C-1. What is ΔrH for this reaction, per mol of Mg?
32
Relationship Involving ΔrH
1. If a chemical equation is multiplied by some factor, then ΔrH is also multiplied by
the same factor.
A + 2B → C ΔrH1
2A + 4B → 2C ΔrH2 =
A + 2B → C ΔrH1
C → A + 2B ΔrH2 =
33
Hess’s Law
The two relationships described on the previous
slide make it possible to determine the ΔrH for a
reaction without directly measuring it in the
laboratory.
Example:
A + 2B → C ΔrH1 = 50 kJ/mol
C → 2D ΔrH2 = -100 kJ/mol
A + 2B → 2D Δ rH 3 =
34
Polling question
Given the following enthalpy data
A + B + 2D → 4E + 2F
A) -25.0 kJ/mol
B) 25.0 kJ/mol
C) -125 kJ/mol
D) 125 kJ/mol
E) 0 kJ/mol
Let’s work a problem
36
Let’s work a problem
37
Determining ΔrHº from Standard Enthalpies of Formation
• The standard state
For a gas: the pure gas at a pressure of exactly 1 bar
For a Liquid or Solid: the pure substance in its most stable form at a pressure
of 1 bar and the temperature of interest (often will be 25 ºC).
38
Determining ΔrHº from Standard Enthalpies of Formation
39
Examples of standard enthalpies of formation
40
Determining ΔrHº from Standard Enthalpies of Formation
41
Calculating ΔrHº
• Using the standard enthalpies of formation we can determine the standard
enthalpy change for a reaction:
42
Let’s work a problem
43
Let’s work a problem
44
Let’s work a problem
45
Polling question
The equations for the complete and incomplete combustion
of octane are given below.
DHf / kJ
25 mol-1
C8 H18 (l) + O2 (g) → 8CO2 (g) + 9H 2O(l)
2 CO -111
17
C8 H18 (l) + O2 (g) → 8CO(g) + 9H 2O(l)
2 CO2 -394
A) Incomplete combustion
B) Complete combustion
46