Problems For Computational Chemistry

From
Atkins: Physical Chemistry for the Life Sciences

http://astro.ins.urfu.ru/sites/default/files/upload_files/temp/1/Physical_chemistr
y_for_the_life_sciences.pdf

Exercises 4.9, 4.11-4.14

Questions 1.3, 1.8, 1.9

Exercises 4.1 and 4.2 and 6.1, 6.2, and 6.5 from Biological Physics by Nelson
N. B. Problem 4.1 parts b and c uses the diffusion law, which you dont need to know.
But going through the derivation for it will reinforce the random walk concepts and
be useful to you in other courses.

Online Problems from Physics for Scientists and Engineers by Young and Freedman
below
for BMS course
https://session.masteringphysics.com/myct/assignmentPrintView?dis...
for BMS course

Due: -You will receive no credit for items you complete after the assignment is due. Grading Policy
The Oxygen Room

A room with dimensions 7.00 m 8.00 m 2.50 m is to be filled with pure oxygen at 22.0 C and 1.00 atm. The
molar mass of oxygen is 32.0 g/mol.
Part A
How many moles noxygen of oxygen are required to fill the room?
Express your answer using three significant figures.
You did not open hints for this part.
ANSWER:
noxygen =
mol
Part B
What is the mass moxygen of this oxygen?
Express your answer in kilograms to three significant figures.
ANSWER:
moxygen =
kg
PSS 18.1 Ideal Gases

Learning Goal:
To practice Problem-Solving Strategy 18.1 Ideal Gases.
Lethal concentrations of gases are often expressed in terms of volume fraction, that is, the fraction of available space
occupied by the hazardous gas. A hazardous-materials worker wants to calculate the volume fraction of chlorine gas in a
storage room after all of the contents of a 0.850-L cylinder of chlorine gas at 137 atm is accidentally released in the
room. The environment in the storage room is kept at a constant pressure of 1.00 atm and a constant temperature of
20.0 C. The room's dimensions are 5.50m 6.00m 2.90m. What is the volume fraction of chlorine gas present in
the storage room?
Problem Solving Strategy 18.1: Ideal Gases
IDENTIFY the relevant concepts:
Unless the problem explicitly states otherwise, you can use the ideal-gas equation for any situation in which you need to
find the state (pressure, volume, temperature, and/or number of moles) of a gas.
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SET UP the problem using the following steps:

1. Identify the variables.
2. In some problems you will be concerned with only one state of the system, in which case the following
equation is the relationship to use.
pV = nRT
Some of the quantities in this equation will be known; others will be unknown. Make a list of what you know
and what you have to find.
3. In other problems you will compare two different states of the same amount of gas. Decide which is state 1
and which is state 2, and make a list of the quantities for each: p1 , p2 , V1 , V2 , T1 , T2 . If all but one of
these quantities are known, you can use the following equation.
p1 V1
T1
Otherwise, use this equation.
p2 V2
T2
= constant (ideal gas, constant mass)

pV = nRT
4. Some problems involve the density (mass per volume) rather than the number of moles n and the volume
V . In this case its most convenient to use the following equation.
pM
RT
EXECUTE the solution as follows:

1. Use a consistent set of units. Sometimes the problem statement will make one system of units clearly more
convenient than others. Decide on your system and stick to it.
2. Don't forget that T must always be an absolute temperature. If you are given temperatures in degrees
Celsius be sure to convert to Kelvin temperatures by adding 273.15. Likewise, p is always the absolute
pressure, never the gauge pressure.
3. You may sometimes have to convert between mass and number of moles n. The relationship is
mtotal = Mn
where M is the molar mass. If you use the following equation, you must use the same mass units for
mtotal and M .
mtotal
RT
M
4. Once you have taken care of steps 13, solve for the target variables.
pV =
EVALUATE your answer:

Look carefully at your results and see whether they make physical sense.
IDENTIFY the relevant concepts

In this problem you are asked to find the volume fraction of chlorine gas in a room. To find the volume fraction you will
need to find the state of the chlorine gas under the conditions of the room. The ideal-gas equation can be used to obtain
this information.
SET UP the problem using the following steps

Part A
Which of the following statements about what happens to the chlorine gas when it leaves the cylinder is true?
ANSWER:
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The pressure of chlorine decreases.

The pressure of chlorine increases.
The pressure of chlorine stays the same.
Part B
What variables for chlorine gas are you given and what variables must you find in this problem?
Drag the appropriate variables to their respective bins.
ANSWER:
EXECUTE the solution as follows

Part C
What is the volume fraction of chlorine in the storage room?
Express the volume fraction numerically.
Hint 1. How to approach the problem

The volume fraction of a specified gas is the fraction of the available space occupied by that gas. To find the
volume fraction of chlorine, determine the volume it would occupy under the conditions of the room if it were
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the only gas present and divide this volume by the total volume of the room.
Hint 2. Find the volume that chlorine gas occupies in the storage room
Calculate the volume V2 that 0.850 L of chlorine gas at 137 atm occupies at 1.00 atm.
Express your answer numerically in liters to four significant figures.
Hint 1. Find an expression for the volume of chlorine gas in the storage room
If a certain amount of gas occupies a volume V1 at a pressure p1 , what is the volume V2 that the
same amount of gas occupies when its pressure is p2 and its temperature hasn't changed?
Express the final volume in terms of p2 , V1 , and p1 .
ANSWER:
V2 =
ANSWER:
V2 =
Hint 3. Find the volume of the storage room

What is the volume of the storage room in liters?
Express your answer numerically in liters to four significant figures.
Hint 1. Find an expression for the volume of the storage room

What is the volume of a room whose shape is a box of length l, width w, and height h?
Express the volume V in terms of l, w, and h.
ANSWER:
V =
Hint 2. Converting between cubic meters and liters

In order to compute the volume fraction, both the volume of the gas and the total volume have to be in
the same units. 1 cubic meter is equal to 1000 liters. Convert the volume of the room into liters.
ANSWER:
V =
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ANSWER:
volume fraction =
EVALUATE your answer

Part D
When you found the volume fraction of chlorine gas present in the storage room, you had to calculate how the
volume of chlorine gas changed as a result of a decrease in pressure. By what factor did the volume of chlorine gas
increase when the gas was released from its container?
Express the ratio of final to initial volumes of chlorine numerically.
ANSWER:
V2
=
V1
Air Bubble Rising in a Lake

A diver named Jacques observes a bubble of air rising from the bottom of a lake (where the absolute pressure is 3.50
atm) to the surface (where the pressure is 1.00 atm). The temperature at the bottom is 4.00 C, and the temperature at
the surface is 23.0 C.
Part A
What is the ratio of the volume of the bubble as it reaches the surface (Vs ) to its volume at the bottom (Vb )?
ANSWER:
Vs
=
Vb
Part B
If Jaques were to hold his breath the air in his lungs would be kept at a constant temperature. Would it be safe for
Jacques to hold his breath while ascending from the bottom of the lake to the surface?
ANSWER:
yes
no
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The Speed of Nitrogen Molecules

The kinetic theory of gases states that the kinetic energy of a gas is directly proportional to the temperature of the gas. A
relationship between the microscopic properties of the gas molecules and the macroscopic properties of the gas can be
derived using the following assumptions:
The gas is composed of pointlike particles separated by comparatively large distances.
The gas molecules are in continual random motion with collisions being perfectly elastic.
The gas molecules exert no long-range forces on each other.
One of the most important microscopic properties of gas molecules is velocity. There are several different ways to
.
describe statistically the average velocity of a molecule in a gas. The most obvious measure is the average velocity v avg
However, since the molecules in a gas are moving in random directions, the average velocity is approximately zero.
Another measure of velocity is (v 2 )avg , the average squared velocity. Since the square of velocity is always positive, this
measure does not average to zero over the entire gas. A third measure is the root-mean-square (rms) speed, v rms , equal
to the square root of (v 2 )avg . The rms speed is a good approximation of the typical speed of the molecules in a gas.
This histogram shows a theoretical distribution of speeds of
molecules in a sample of nitrogen (N2 ) gas. In this problem,
you'll use the histogram to compute properties of the gas.
Part A
What is the average speed v avg of the molecules in the gas?
Express your answer numerically to three significant digits.
ANSWER:
vavg =
m/s
Part B
Because the kinetic energy of a single molecule is related to its velocity squared, the best measure of the kinetic
energy of the entire gas is obtained by computing the mean squared velocity, (v 2 )avg , or its square root v rms . The
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quantity v rms is more common than (v 2 )avg because it has the dimensions of velocity instead of the less-familiar
velocity-squared.
What is the rms speed v rms of the molecules in the nitrogen gas?
Express your answer numerically to three significant digits.
ANSWER:
m/s
vrms =
Part C
What is the temperature T of the sample of N2 gas described in the histogram?
Express your answer in degrees Celsius to three significant figues.
ANSWER:
T=
Gas Scaling
When doing numerical calculations involving temperature, you need to pay particular attention to the temperature scale
you are using. In general, you should use the Kelvin scale (for which T = 0 represents absolute zero) in such
calculations. This is because the standard thermodynamic equations (i.e., the ideal gas law and the formula for energy of
a gas in terms of temperature) assume that zero degrees represents absolute zero.
If you are given temperatures measured in units other than kelvins, convert them to kelvins before plugging them into
these equations. (You may then want to convert back into the initial temperature unit to give your answer.)
Part A
The average kinetic energy of the molecules of an ideal gas at 10 C has the value K10 . At what temperature T1 (in
degrees Celsius) will the average kinetic energy of the same gas be twice this value, 2K10 ?
Express the temperature to the nearest integer.
ANSWER:
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T1 =
Part B
The molecules in an ideal gas at 10 C have a root-mean-square (rms) speed v rms . At what temperature T2 (in
degrees Celsius) will the molecules have twice the rms speed, 2v rms ?
Express the temperature to the nearest integer.
ANSWER:
T2 =
An Expanding Monatomic Gas

We start with 5.00 moles of an ideal monatomic gas with an initial temperature of 128 C. The gas expands and, in the
process, absorbs an amount of heat equal to 1280 J and does an amount of work equal to 2120 J .
Part A
What is the final temperature Tfinal of the gas?
Use R = 8.3145 J/(mol K) for the ideal gas constant.
ANSWER:
Tfinal =
Work Done by an Expanding Gas

Learning Goal:
To derive the expression for the work done by an expanding gas, dW = p dV , and to understand how it follows from the
expression W = F d for mechanical work.
Especially from the historically important perspective of making engines to convert heat energy into work, the work in
thermodynamics is defined as the work done by the system on the exterior world, and not vice versa as is done in the
rest of classical mechanics. In classical mechanics, one always considers the work done on a system by the outside
world. Rarely does one think about the work done by the system. Suppose you push a large block with a certain force of
magnitude F over some distance. You have done work on the block; hence the energy of the block should increase.
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According to Newton's 3rd law, the block exerts the same magnitude of force F , but in the opposite direction (i.e.,
directed back at you). Hence, the work done by the block (on you) is negative, since the direction of motion opposes the
direction of the force. In summary, you have to be careful about the sign of the work: the same situation gives opposite
signs of the work depending on whether our perspective is classical mechanics or thermodynamics.
In thermodynamics, one often deals with liquids and gases that exert forces on their containers (i.e., the fluids exert
pressure over an area). If the container changes volume, then this force acts through a distance and hence does work.
For a steam engine, the example pictured here, the "container"
is a cylinder whose volume changes as the piston slides in or
out. Suppose a gas is confined within the cylinder. The
pressure of the gas is p, and the area of the cylinder is A.
Consider the work done as the gas expands, pushing the
piston to the right. Call the infinitesimal distance the piston
moves dx.
Part A
What force F does the gas exert on the piston? (Note that the positive x axis is to the right in the figure.)
Express the force in terms of p, A, and any constants,
ANSWER:
F=
Part B
If the piston moves a distance dx, what is dW , the work done by the gas?
Express the work done by the gas in terms of given quantities.
ANSWER:
dW =
Part C
What is dV , the increase in volume of the gas?
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Express the differential increase in terms of dx and other given quantities.

ANSWER:
dV =
Part D
Now find the work done by the gas in terms of the thermodynamic variables.
Express the differential work dW in terms of thermodynamic variables such as the gas's pressure p,
temperature T , volume V , and its change in volume dV .
ANSWER:
dW =
Part E
Suppose that the gas expands from V0 to V1 at constant pressure p0 . How much work W is done by the gas?
Express the work in terms of p0 , V0 , and V1 .
ANSWER:
W=
Part F
Is the work you just computed positive or negative?
ANSWER:
positive
negative
Part G
Assume now that the diameter of the piston is reduced by a factor of 2. What is the amount of work W2D done by a
gas of pressure p0 in expanding from the same initial volume V0 to the same final volume V1 ? Note that the piston
has to start out much farther to the right for the volume to be V0 initially.
Express your answer in terms of p0 , V0 , V1 , and simple numerical factors.
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ANSWER:
W2D =
Increasing Entropy
Quantity A of an ideal gas is at absolute temperature T , and a second quantity B of the same gas is at absolute
temperature 2T . Heat is added to each gas, and both gases are allowed to expand isothermally.
Part A
If both gases undergo the same entropy change, is more heat added to gas A or gas B?
ANSWER:
More heat is added to gas A.
More heat is added to gas B.
The same amount of heat is added to each gas.
Assume that gas A and gas B receive the same amount of heat as in the process described in Part A.
Part B
If both gases were initially at the same absolute temperature, would they still undergo the same entropy change?
Hint 1. How to approach the problem

Use your results from Part A and remember that the entropy change in an isothermal process is proportional
to the amount of heat added to or removed from the system.
ANSWER:
No, gas A would undergo the greater entropy change.
No, gas B would undergo the greater entropy change.
Yes, both gases would have the same entropy.
From Hot to Cool: The Second Law of Thermodynamics

Learning Goal:
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To understand the meaning and applications of the second law of thermodynamics, to understand the meaning of
entropy, and perform some basic calculations involving entropy changes.
The first law of thermodynamics (which states that energy is conserved) does not specify the direction in which
thermodynamic processes in nature can spontaneously occur. For example, imagine an object initially at rest suddenly
taking off along a rough horizontal surface and speeding up (gaining kinetic energy) while cooling down (losing thermal
energy). Although such a process would not violate conservation of energy, it is, of course, impossible and could never
take place spontaneously.
The second law of thermodynamics dictates which processes in nature may occur spontaneously and which ones may
not. The second law can be stated in many ways, one of which uses the concept of entropy.
Entropy
Entropy can be thought of as a measure of a system's disorder: A lower degree of disorder implies lower entropy, and
vice versa. For example, a highly ordered ice crystal has a relatively low entropy, whereas the same amount of water in a
much less ordered state, such as water vapor, has a much higher entropy. Entropy is usually denoted by S , and has units
of energy divided by temperature (J/K). For an isothermal process (the temperature of the system remains constant as
it exchanges heat with its surroundings), the change in a system's entropy is given by
Q
,
T
where Q is the amount of heat involved in the process and T is the absolute temperature of the system. The heat Q is
positive if thermal energy is absorbed by the system from its surroundings, and is negative if thermal energy is
transferred from the system to its surroundings.
S =
Using the idea of entropy, the second law can be stated as follows:
The entropy of an isolated system may not decrease. It either increases as the system approaches equilibrium, or stays
constant if the system is already in equilibrium.
Any process that would tend to decrease the entropy of an isolated system could never occur spontaneously in nature.
For a system that is not isolated, however, the entropy can increase, stay the same, or decrease.
Part A
What happens to the entropy of a bucket of water as it is cooled down (but not frozen)?
ANSWER:
It increases.
It decreases.
It stays the same.
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Part B
What happens to the entropy of a cube of ice as it is melted?
ANSWER:
It increases.
It decreases.
It stays the same.
Part C
What happens to the entropy of a piece of wood as it is burned?
ANSWER:
It increases.
It decreases.
It stays the same.
Let us try some calculations now.
Part D
An object at 20 C absorbs 25.0 J of heat. What is the change in entropy S of the object?
Express your answer numerically in joules per kelvin.
ANSWER:
S =
J/K
Part E
An object at 500 K dissipates 25.0 kJ of heat into the surroundings. What is the change in entropy S of the
object? Assume that the temperature of the object does not change appreciably in the process.
ANSWER:
S =
J/K
Part F
An object at 400 K absorbs 25.0 kJ of heat from the surroundings. What is the change in entropy S of the object?
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Assume that the temperature of the object does not change appreciably in the process.
ANSWER:
S =
J/K
Part G
Two objects form a closed system. One object, which is at 400 K, absorbs 25.0 kJ of heat from the other
object,which is at 500 K. What is the net change in entropy Ssys of the system? Assume that the temperatures of
the objects do not change appreciably in the process.
ANSWER:
Ssys =
J/K
Entropy Change in a Free Expansion: A Microscopic View

A thin partition divides a thermally insulated vessel into a lower compartment of volume V and an upper compartment of
volume 2V . The lower compartment contains n moles of an ideal gas; the upper part is evacuated.
Part A
When the partition is removed, the gas expands and fills both compartments. How many moles n of gas were initially
contained in the lower compartment if the entropy change of the gas in this free-expansion process is 17.28 J/K?
Express your answer to three significant figures.
ANSWER:
n=
mol
Score Summary:
Your score on this assignment is 0.0%.
You received 0 out of a possible total of 10 points.
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Problems For Computational Chemistry

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Problems For Computational Chemistry

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From

Atkins: Physical Chemistry for the Life Sciences

for BMS course

for BMS course

The Oxygen Room

PSS 18.1 Ideal Gases

for BMS course

SET UP the problem using the following steps:

= constant (ideal gas, constant mass)

EXECUTE the solution as follows:

EVALUATE your answer:

IDENTIFY the relevant concepts

SET UP the problem using the following steps

for BMS course

The pressure of chlorine decreases.

EXECUTE the solution as follows

Hint 1. How to approach the problem

for BMS course

Hint 3. Find the volume of the storage room

Hint 1. Find an expression for the volume of the storage room

Hint 2. Converting between cubic meters and liters

for BMS course

EVALUATE your answer

Air Bubble Rising in a Lake

for BMS course

The Speed of Nitrogen Molecules

for BMS course

for BMS course

An Expanding Monatomic Gas

Work Done by an Expanding Gas

for BMS course

for BMS course

Express the differential increase in terms of dx and other given quantities.

for BMS course

Hint 1. How to approach the problem

From Hot to Cool: The Second Law of Thermodynamics

for BMS course

for BMS course

Let us try some calculations now.

for BMS course

Entropy Change in a Free Expansion: A Microscopic View

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