CHEM*1050 – General Chemistry II

Calculus
Atoms
Molecules Statistical
Bonding & Structures Methods Bulk Properties
Spectroscopy Solution Equilibria
Differential Equations
Quantum mechanics Thermodynamics
Electrochemistry CHEM*1050
Kinetics Material
Differential Equations
Matrix Algebra

Week 1 – Textbook sections to read. Answer the questions below to start to make notes.
Thermochemistry
6.1 Energy and Its Units
# Define energy, kinetic energy, potential energy, and internal energy.
# Define the SI unit of energy joule, as well as the common unit of energy calorie.
# Calculate the kinetic energy of a moving object.
# State the law of conservation of energy.

6.2 First Law of Thermodynamics: Work and Heat

# Define a thermodynamic system and its surroundings.
# Define work and heat.
# Define the change of internal energy of a system.
# Express the first law of thermodynamics verbally and mathematically.

6.3 Heat of Reaction; Enthalpy of Reaction

# Define heat of reaction.
# Distinguish between an exothermic process and an endothermic process.
# Describe pressure-volume work verbally and mathematically.
# Define enthalpy and enthalpy of reaction.
# Relate the heat of reaction at constant pressure and the enthalpy of reaction.

6.6 Measuring Heats of Reaction

# Define heat capacity and specific heat.
# Relate the heat absorbed or evolved to the specific heat, mass, and temperature change.
# Calculate using this relation between heat and specific heat.
# Define calorimeter.
# Calculate the enthalpy of reaction from calorimetric data (its temperature change and heat
capacity)

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Introduction to THERMODYNAMICS

What is thermodynamics?

What are some types of energy?

Why is thermodynamics important? How is it related to sciences other than chemistry?

Studying thermodynamics can help answer questions such as the following:

Interconversion of energy – how? Why? etc.
Is a particular reaction possible?
How much useful work can be obtained from a reaction?
Can we understand chemical equilibria?

Chemical reactions involve a transfer of energy between the SYSTEM and

SURROUNDINGS

DEFINITIONS:

What is the SYSTEM?

What does it mean if we call the system

Open?

Closed?

Isolated?

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What are the SURROUNDINGS?

What do we get if we add the system and surrounding?

What do we mean by the “STATE” of a system?

What are STATE VARIABLES?

What do we mean if we say a state variable is Intensive?

What are some examples of intensive properties?

What do we mean if we say a state variable is Extensive?

What are some examples of extensive properties?

ENERGY TRANSFER
The INTERNAL ENERGY of the system may change if we transfer energy in and out of a
system. What do we mean by internal energy? What symbol do we use for internal energy?

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What are the Two ways internal energy can change? What are the symbols for these
quantities?

Note: Another way is by adding or removing mass but this is not encountered in a
“closed” system.

Think about how these forms of ENERGY TRANSFER might be expressed as a

diagram.

Can we measure the absolute value of the internal energy?

What can we determine? How can this be expressed as an equation?

Based upon the conservation of energy:

State the 1st LAW OF THERMODYNAMICS
In words:

As an equation:

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HEAT ENERGY, HEAT TRANSFER and TEMPERATURE
Can we create or destroy energy? What can we do with it?

What do we mean by the word TEMPERATURE?

How does heat flow?

How is temperature related to molecules?

THERMOCHEMISTRY (Chapter 6)
What is thermodynamics?
What is studied

CHEMICAL REACTIONS AND ENERGY CHANGES

When a chemical reaction occurs is there an ENERGY CHANGE?

How can we recognize an energy change in a chemical reaction? Give an example.

What is an exothermic reaction? What happens during this type of reaction? Give an
example.

What is an endothermic reaction? What happens during this type of reaction? Give an
example.

Is heat an intensive or extensive property?

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SIGN CONVENTION FOR HEAT PROCESSES

If heat is absorbed by the system what sign do we give it? Where does this heat come from?

If heat is given off by the system what sign do we give it? Where does this heat go?

Most reactions are run under constant pressure conditions (including biological processes).
What do we call the heat given off (or absorbed) at constant pressure?
What symbol do we use for this?

What equation do we use for this change in heat?

EXOTHERMIC and ENDOTHERMIC PROCESSES

Try and express the concepts of exothermic and endothermic processes as diagrams

Heat changes at constant P are equal to the change in?

If heat is given off, the rxn is? What is the sign of H?

If heat is absorbed, the rxn is? What is the sign of H?

What is calorimetry? What do we measure?

What can we associate this measurement with?

How do we do that?

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What is HEAT CAPACITY? What is the symbol we use?

What is the difference between the following – what symbols are used for each? What units
are used for each?
Heat Capacity

Molar Heat Capacity

Specific Heat

How can these be used to calculate q?

Do you have to memorize 3 equations? How are they the same?

In calorimetry∙ the idea is to ISOLATE the SYSTEM from the SURROUNDINGS.

e.g. "Coffee–Cup" Calorimeter – refer to Figure 6.15 in text

What do we measure in the coffee-cup calorimeter? How do we use this information?

You will use a coffee-cup calorimeter in the second “wet” lab this semester.

How is the heat released in the reaction related to the heat gained by the surroundings?
How can we express this as an equation? How is this related to enthalpy?

What is HEAT OF SOLUTION?

Example – Dissolution of a solid (KF) in water:

Exactly 1.23 g KF (s = 0.84 J∙g–1∙deg–1) is dissolved in 10.0 g H2O (s = 4.184 J∙g–1∙ deg–1).
The H2O temp rises from 23.2 to 33.1 
KF = 58.1 g mol–1)

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KF dissolves in the water and liberates heat which warms the solution.

Energy =

How do the size of q(KF) and q(H2O) compare to each other?

MM for KF = 58.1 g/mol, therefore # moles of KF added =

1 mole of KF would therefore evolve _______________________ of heat.

Example 2 – Transfer of heat (no chemical reaction):

–1 –1
50.0 g Cu (c = 24.5 J K mol ) is heated to 100C and then placed in 250 g H2O (s =
4.184 J g–1K–1) at 0.0C. What is final temp of H2O (in C)?
# moles of copper =
Let Tf(C) represent the final temperature
Loss of heat from copper = Gain of heat in water

Bomb Calorimeter (refer to Figure 6.16)

What is different between a bomb calorimeter and a coffee cup calorimeter? What conditions
are different?

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Example:
Exactly 1.00 g of (CH3)2N2H2 (MM = 60.1 g/mol) is burned in a bomb calorimeter with a
heat capacity = 1840 J∙deg–1. A 5.00 kg water bath rises in temperature from 24.62 to
26.07C. Calculate the energy released when 1 mole is burned.

Total heat produced = warms bomb + warms water bath

1 mole of (CH3)2N2H2 evolves ____________________________ kJ of heat energy.

EXTRA PROBLEMS TO TRY
Problem 1:
50.0 mL dilute AgNO3 is added to a solution with OH– ions in a coffee cup calorimeter.
Ag2O precipitates and the temperature of the liquid goes from 23.78 to 25.19C. Assume
that the mixture has the same specific heat as water. Calculate "qsurr" for a mass of 150.0 g. Is
the reaction exothermic or endothermic?
Answer: qSurroundings = 885 Joules
Rxn exothermic (temp rose).

Problem 2:
A 48.9 g sample of metal at 95.72C is added to 43.58 g H2O at 23.84C. The final
temperature of the metal + water is 28.37C. What is the metal’s specific heat in J∙g–1∙deg–1?
Answer: s = 0.251 J∙g–1∙deg–1

Problem 3:
When ice at 0C melts to liquid H2O, it absorbs 334 J per gram. The specific heat of water
is 4.184 J∙g–1∙deg–1. Suppose the heat needed to melt a 35.0g ice cube is absorbed from water
(0.210 kg) in a calorimeter at 21.0C. What is the final water temperature? [This is the kind
of calculation that all experienced party givers do before throwing a party!]
Answer: TFinal = 6.6C

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WHAT ABOUT WORK?

The first law of thermodynamics states that the change in the internal energy is dependent
upon the flow of heat, but is also depend on WORK.

What is WORK? What symbol do we use? Give some examples of work.

COMPRESSION/EXPANSION or P-V WORK (see Figs 6.5 & 6.6)

What is the equation for when at a CONSTANT extension pressure, Pext., the work (in
Joules) done BY the surroundings ON a gas (i.e., system)?

Since Compression is work is done ON the system BY the surroundings what change do
we have to make to account for a change in energy of the system?

What is the sign of work done of the system? What is the sign of work done by the system?

Pressure-Volume (or P-V) work is the most common type of work encountered in chemical
systems.

UNITS FOR ENERGY

Hence PV → Pa•m3 = Joule
An older unit still in use is the “calorie”, where 1 cal = 4.184 J (by definition)

EXAMPLE: Calculate the work at 25C and 1.00 atm for

a) CO2(g) + NaOH(s)  NaHCO3(s)
b) 2O3(g)  3O2(g)

Consider:
– only PV work,
– that the gases behave ideally (i.e., follow the ideal gas law) and
– the equations represent the amounts in moles.

How can we put these ideas together to one equation?

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QUESTIONS:
1) A gas sample is heated in a cylinder using 550 kJ of heat. A piston compresses the
gas, doing 700 kJ of work. What is the change in internal energy of the system?

2) Calculate the work done when 6300 L of an ideal gas (initially at 1.00 atm) is
compressed (at constant T) by a constant pressure of 1.40 atm to a final volume of
45L.

Note: The gas constant R = 8.314 J K-1 mol-1 = 0.0821 L•atm K–1•mol–1

SIGN CONVENTION FOR WORK and HEAT PROCESSES

PROCESS SIGN
Work done BY the system ON the surroundings (expansion) –

Work done ____ the system ____ the surroundings (____________) +

Heat absorbed BY the system FROM the surroundings (endothermic) +

Heat absorbed ____ the system ____ the surroundings (____________) –

• if w and q are positive, they tend to increase U of the system

• work done by the system is a reduction in U, hence negative.

INTERNAL ENERGY & ISOTHERMAL EXPANSIONS

• Internal energy of an ideal gas depends only on its temperature.
• To change the temperature of a gas, the internal energy must be changed by doing
work on it or transferring energy to it, i.e., U = q + w.
• When a gas expands, the forces due to pressure push the container walls back, so the
gas is doing work. Change in w is negative.
• For an isothermal (i.e., T = 0) expansion of an ideal gas, ∆U = 0 because the kinetic
energy of the gas is related to its temperature (which here is unchanged) and the
potential energy is related to bonding and structure (which here is unchanged).
• Since U = q + w = 0, ∴ w = –q. The system does w joules of PV-work and
absorbs an equivalent amount of heat q = –w.

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HEAT CHANGES IN REACTIONS
a) Reactions at Constant Volume, i.e., a sealed container
If the system cannot expand or compress what is V? What is the amount of work?
How does this relate to a change in internal energy?

What is q at constant volume? What type of calorimeter is this?

b) Reactions at Constant Pressure, i.e., open to the atmosphere

What is V? Is any work done? How can we calculate the amount of work done?
How does this relate to enthalpy and internal energy?

What is a state function? Give examples of things that are state functions and things that are
not. Can you show state function as a diagram?

HOW DO H and U COMPARE FOR A REACTION?

Example:
At 298 K, CH4(g) + 2O2(g)  CO2(g) + 2H2O(l), HRxn = –890.6 kJ mol–1
What is URxn?

URxn =

Could calculate the actual volume change from PV = nRT.

Not necessary (in this case), since we can use PV = nRT.

n =

U =

Net result is a shrinking volume (compression), therefore work done by

____________________ on _________________________.

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PROBLEM:
When an ideal gas expands at constant temperature (i.e., isothermal expansion), U is zero.
Consider 1.00 L of an ideal gas initially at 9.00 atm and 15 C.
(a) Calculate q and w if the gas expands isothermally against a pressure of 1.00 atm.
(b) Calculate q and w if the gas expands isothermally first against a pressure of 3.00 atm.
And then against 1.00 atm.
(c) Calculate q and w if the gas expands isothermally first against a pressure of 3.00 atm,
then 2.00 atm and then against 1.00 atm.
(d) Comment on the results.
Answers:
a) q = –w = +0.810 kJ
b) w1 + w2 = –1.216 kJ
q1 + q2 = +1.216 kJ
c) w = w1 + w2 + w3 = –1.368 kJ
q = q1 + q2 + q3 = +1.368 kJ
d) The conclusion is that you would get the maximum amount of work done on the surroundings
by doing the expansion in an infinite number of very small steps.

MC Questions

1. Label the following process as exothermic or endothermic:

a) Your hand gets cold when you touch ice.
b) Water vapour condenses on a cold pipe.

2. Which of the following is (are) TRUE?

a) A thermally isolated rxn vessel becomes warmer when an endothermic reaction occurs.
b) An exothermic reaction is characterized by a negative value of H at constant
P.
c) Heat is evolved when an exothermic reaction occurs.
A) a only B) b only C) a & b only D) b & c only E) a, b, & c

3. For the reaction: ½A2(aq) + ½B2(aq) AB(aq); H° = -265 kJ/mol, if solutions A2 and B2,
starting at the same temp., are mixed in a coffee-cup calorimeter, the reaction that occurs is
A) Exothermic and T of the resulting solution rises.
B) Endothermic and T of the resulting solution rises.
C) Exothermic and T of the resulting solution falls.
D) Endothermic and T of the resulting solution falls.

4. Two different metals of equal mass with different specific heat capacities absorb the same
amount of heat. Which undergoes the smallest change in temperature?
A) metal with higher specific heat capacity
B) metal with lower specific heat capacity
C) Because they have equal mass, both metals undergo the same change in temperature.
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5. A 50.0 g sample of water at 80°C is added to a 100.0 g sample of water at 20°C. The final
temperature of the water should be
A) between 20°C & 50°C. B) 50°C. C) between 50°C & 80°C.

6. Calculate the work needed to make room for products in the combustion of 1 mole of C3H8(g)
to CO2 and water vapour where reactants and products are brought to STP.
A) +2.48 kJ B) +2.27 kJ C) –2.27 kJ D) –2.48 kJ E) no work is required

7. Calculate the change in internal energy for a system that does 500 kJ of work on the
surroundings when 300 kJ of heat are absorbed by the system.
A) – 800 kJ B) – 200 kJ C) 0 kJ D) +50 kJ E) +75 kJ

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