You are on page 1of 16

General Chemistry

1
Gases and Thermochemistry

Module 003 : Gases and Thermochemistry


In this module, we will study about gases, explore the relationships among
pressure, temperature, volume and amount, and use these

This week, we will discuss gases and itscharacteristic,behavior, and the laws
associated to it. We will also discuss about thermochemistry – the branch of
chemistry which explains how energy changes during chemical reactions.

At the end of this module, you will be able to:

1. Identify the characteristics of a gas


2. Describe the pressure of a gas and ways of measurement
3. Explain the relationship among temperature, pressure, volume and
amount of gas and differentiate Gas Laws
4. Explain the behavior of gas using the Ideal Gas Law
5. Understand the partial pressure of gases in a mixture
6. Explain how gases behave as explained by the kinetic molecular theory
7. Describe energy and distinguish its different forms
8. Understand the relationship between energy, work, and heat
9. Understand how internal energy and its changes are measured
10. Know the basics of calorimetry

Gases

As discussed in the previous modules, gases like solids and liquids are also
considered a phase of matter.Gases are less complex than solids and liquids
in many forms – forces in between gas molecules are relatively weak, thus, its
molecules move in a random motion, freely and independently of each other.
When exposed to temperature and pressure changes, behavior of gases can
be easily predicted.

All gases possess the following physical characteristics:


 Gases take up volume and shape of its container
 Gases are considered the most compressible state of matter
 When kept in a single container, gases will mix uniformly and totally
 Gases have the lowest density compared to solids and liquids

Some solids and liquids on ordinary conditions can also appear in a gaseous
state. These are identified as vapors. For example, water (H2O) can exist as
solid ice, liquid water, or water vapor.

Course Module
Table below shows some common compounds that are gases at room
temperature.

Figure 1.Some common compounds that are gases at room temperature;


http://schoolbag.info/chemistry/central/central.files/image1293.jpg; April 26, 2017

Pressure of Gas
Pressure is defined as the effect of a force applied to a surface. Measurement
can be done by means of using a barometer or manometer.

Pressure (Pa)–the effect of a force applied to a surface


The SI unit of pressure is pascal (Pa)*.

P = (Force) F
(Area) A

*1 Pascal is equal to 1 newton per square meter (N/m2)


1 Pa = 1 N/m2

Atmospheric pressure

Atmospheric pressure is the pressure exerted by Earth’s atmosphere which


depends on temperature, location and weather conditions.
The direction goes upward, downward and both sides, like fluid, air travels to
many directions. As air travels, its molecules collide with any surface which it
comes contact with.
How do we measure atmospheric pressure?
General Chemistry
3
Gases and Thermochemistry

1. Barometer – most popular device used to measure atmospheric


pressure. It is composed of a long tube made of glass, which is closed
on the other end and filled with mercury. Once the tube is carefully
turned upside down in a dish of mercury, a vacuum at the top will be
formed.

Figure 2. Mercury barometer;


http://cdn.thinglink.me/api/image/649270600426061825/1024/10/scaletowidth/0/0/1/1/false/tr
ue?wait=true; April 26, 2017

2. Manometer – is an instrument measuring the pressure of gases


contained in an apparatus

2 Types of Manometer:
1. Closed-tube – measures pressure below atmospheric pressure
2. Open-tube – measures pressure equal to or greater than the
atmospheric measure

Figure 3. Manometer; https://saylordotorg.github.io/text_general-chemistry-principles-patterns-and-


applications-v1.0/section_14/c847224dff75ece78784d0d76aeaae8c.jpg; April 26, 2017

Course Module
Gas Laws

4 quantities must be known in order to identify the physical condition of a


gas:
1. Temperature
2. Pressure
3. Volume
4. Amount of gas (expressed in number of moles)

Relationships among these 4 quantities are expressed by means of Gas Laws,


which are the following:

1. The Pressure-Volume Relationship: Boyle’s Law– states that at a


constant temperature, the volume of a fixed amount of gas is inversely
proportional to its pressure. This means that if pressure increases, the
volume of gas decreases, and vice versa.

1
V = constant x or PV = constant
p

*value of constant depends upon temperature and amount of gas

2. The Temperature – Volume Relationship: Charle’s Law – states


that at constant pressure, the volume of a fixed amount of gas is
directly proportional to its absolute temperature (expressed in Kelvin,
not in degrees Celsius). This means that if the absolute temperature
increases, the volume of gas also increases.

V
V = constant x T or constant = T
*value of constant depends on the pressure and amount of gas

3. The Quantity-Volume Relationship: Avogadro’s Law – states that


at constant temperature and pressure, volume of gas is directly
proportional to the number of moles of gas present. This means that if
the number of moles of gases increases, the volume of gas also
increases, given that the temperature and pressure are constant.

V
V = constant x n or constant = 𝑛

*n = number of moles
General Chemistry
5
Gases and Thermochemistry

Figure 4.Summary of Gas Laws; https://image.slidesharecdn.com/chapter5notes-150901140506-


lva1-app6892/95/chapter-5-notes-25-638.jpg?cb=1441116453; April 26, 2017

Ideal Gas Equation

The Ideal Gas Equation (or also called the Ideal Gas Law) is a combination of
laws of Boyle, Charle and Avogadro. These laws were expressed individually
as:

Boyle’s law V∝ _1_


P (constant n, T)

Charles’s law V∝T (constant n, P)

Avogadro’s law V∝n (constant T, P)

When these expressions are combined, it is expressed as:

V∝ _nT_
P

Course Module
The proportionality constant is referred to as the gas constant. It is denoted
by the letter R. Thus, the equation becomes:
𝑛T
V=R ( )
P

Above equation can be rearranged and the Ideal Gas Law is expressed as:

PV=nRT

An ideal gas is defined as a hypothetical gaseous substance in which


relationship among pressure, volume and temperature istotally described by
the ideal gas law.

In order to use the Ideal Gas Law, the gas constant R needs to be known.
Image below shows the numerical values of the gas constant R, in various
units.

Figure 5. Numerical values of the Gas Constant, R, in various units;


http://wps.pearsoncustom.com/wps/media/objects/3033/3106029/fg10_T02.jpg; April 26, 2017

Dalton’s Law of Partial Pressures


In our previous discussion, we have focused on the characteristics of pure
gases with only 1 substance. However, what happens when 2 or more
different gases combine together?
Dalton’s law of partial pressures states that, the total pressure of the
combination of gases is the sum of the pressures of each of the component
gases. Partial pressure is defined as the amount of pressure exerted by each
component gas in amixture, which is independent of the pressure exerted by
the other gases.

Thus, Dalton’s law of partial pressures is written as:


Pt = P1 + P2 + P3 + P4 + P5 ….
General Chemistry
7
Gases and Thermochemistry

where, Pt is the total pressure of a gas mixture and P1, P2, P3, P4, P5 and so on,
are the partial pressures of each component gases.

Using the ideal gas law, we can write:


RT RT RT RT RT
P1 = 𝑛1 ( V ); P2 = 𝑛2 ( V ); P3 = 𝑛3 ( V ); P4 = 𝑛4 ( V ); P5 = 𝑛5 ( V ); and so
on
where n = number of moles of each gas

Gases contained in one container will occupy the same volume and exposed
to same temperature, thus,
RT RT
Pt = (n1 + n2 + n3 + n4 + n5 + …)( V ) = nt( V )

Thus, atconstant temperature and volume, the total pressure of a gas is


directly proportional to the number of moles of gas present.

Figure 6.Dalton’s Law of Partial Pressures;


https://www.alcaweb.org/arch.php/resource/view/86033; April 26, 2017

Kinetic Molecular Theory of Gases


In the previous discussion, you have learned about how gases behave. In this
section, the Kinetic Molecular Theory of Gases (also referred to as the
theory of moving molecules) will help you understand why gases behave as
they do. This theory was developed by Rudolf Clausius (1822 – 1888) in
1857.

Course Module
This theory provides a molecular explanation of both pressure and
temperature. The pressure of a gas is produced when molecules collide with
the container walls. The number of times and degree of hardness the
molecules collide with the walls determine the magnitude of the pressure.
The average kinetic energy of the gas molecules determines the absolute
temperature of a gas. If different gases are kept at the same temperature,
they have the same average kinetic energy.Once the temperature is doubled,
the average kinetic energy will also double.

Kinetic molecular theory is summarized as follows:


1. Gases are composed of large numbers of molecules that are in
constant, random motion.
2. Total volume of all the gas molecules is negligible in relation to the
total volume where the gas is contained.
3. Forces between gas molecules, whether attractive or repulsive, are
negligible.
4. Energy can be transferred when molecules collide with one another.
However, at constant temperature, the average kinetic energy
remains unchanged.
5. Average kinetic energy of gas molecules is proportionate to absolute
temperature. At any given temperature, gas molecules have exactly
similar average kinetic energy.

Thermochemistry
Thermochemistry is the branch of chemistry that explains energy changes
that occur during chemical reactions. Thermodynamics on the other handis
the study of energy and how it changes. Further details on thermodynamics
will be discussed in the next modules.

Nature of Energy
Since energy comes in many forms, it can only be observed and measured by
its effect on matter.

Kinetic and Potential Energy


Kinetic energy is an energy object possesses due to its motion, and is
expressed as:

1
𝐸𝑘 = 𝑚𝑣 2
2

where, Ek = magnitude of kinetic energy


m= mass
v = speed

As the mass or speed increases, kinetic energy also increases.


General Chemistry
9
Gases and Thermochemistry

Potential energy is an energy caused by the relative position of an object. It


is also referred to as the “stored” energy resulting from the attractions and
repulsions of an object from another object.

There are times in which potential energy is transformed into kinetic energy.
See illustration below:

Figure 7.Kinetic and potential energy;


http://www.ryansearch.net/blog/march_2015/kinetic_vs__potential_leadership; April 26, 2017

Units of Energy
Joule (J) is the SI unit of energy, and is defined as 1 J = 1 (kg-m2)/s2. Another
unit being used is calorie (cal), and is defined as the amount of energy
needed in order to raise the temperature of 1 g of water by 1°C. Calorie is
defined as 1 cal = 4.184 J.

Transferring Energy: Work and Heat


Energy is defined as the capacity to do work. Energy changes in 2 forms – in
the form of work and in the form of heat.

1. Work is defined as an energy used to move an object against a force;


force is any push or pull exerted on a given object
Work is expressed as:
work = force x distance
w=Fxd
2. Heat is the energy used to cause the temperature of an object to
increase. Temperature is measure of thermal energy an object
contains.
Course Module
System and surroundings
System – well-defined portion in which we are interested in
Surroundings – the rest or everything else apart from the system

In a laboratory, the system is the reactants and products being used, while
the surroundings is the container and all things beyond it.

There are 3 kinds of systems:


1. Open – can exchange matter and energy with its surroundings.
Example is an uncovered pot of boiling water, wherein the stove
provides heat to the system and water is released in the form of steam
or vapor
2. Closed – can exchange energy but not matter with its surroundings.
Example is a mixture of hydrogen and oxygen gas in a cylinder fitted
with a piston. The hydrogen and oxygen atoms are the system, while
the cylinder and everything beyond it is the surroundings. In this
case, a chemical reaction will occur on the hydrogen and oxygen
atoms in the system, but it will not exchange any matter with its
surroundings (unless the piston is pulled upward).
3. Isolated – neither energy nor matter can be exchanged with its
surroundings. Example is an insulated thermos which contains hot
coffee. However, the coffee will eventually cool, thus it is not a perfect
isolation.

The First Law of Thermodynamics


Energy can neither be created nor destroyed. The amount of energy lost by a
system is equal to the amount of energy gained by its surroundings and vice
versa. The first law of thermodynamics states that energy is conserved.

Internal Energy
The total of all the kinetic and potential energies in a system is referred to as
the internal energy (E).

Change in internal energy is expressed as:

ΔE = Efinal– Einitial

where; ΔE – difference between the final and initial internal energy in a


system
positiveΔE – energy is gained by the system from the surroundings
negativeΔE – energy is lost by the system to its surroundings
General Chemistry
11
Gases and Thermochemistry

Relating ΔE to Heat and Work


The energy in a system can cause change with its surroundings when heat is
added or work is done. If there is no heat applied or no work done, the
internal energy will not change.

The total of the heat (q) applied to or from the system and the work (w) done
on or by the system may be expressed as:

ΔE=q + w

The internal energy of a system increases when we put heat or work into it.

Endothermic and Exothermic Processes


Endothermic – a process in which heat is transferred from the surroundings
into a system (endo means “into). Example is ice melting – where the system
absorbs heat from its surroundings

Exothermic –a process in which heat is transferred from a system to its


surroundings (exo means “out of”). Example is the combustion of a gasoline,
where heat goes out of the system to its surroundings.

State Functions
Internal energy is a state function. It depends only on the present state, and
not on its history or the path by which the system arrived at that state. Thus,
ΔE is dependent only on Einitialand Efinal, and not how the change occurs.

Figure 8. State Functions;


http://wps.prenhall.com/wps/media/objects/3311/3390593/blb0502.html; April 26, 2017

Course Module
Enthalpy
Enthalpy (H) – described as the sum of the internal energy(E) and product of
pressure (P) and volume (V) in a system. It is expressed as:

H = E + PV

where; H, E, P and V are all state functions

Pressure – Volume Work


Pressure – Volume Work (P-V work) is defined as the work involved when
gases expand or compress. At constant pressure, this is expressed as:

w =P Δ V
where; P = pressure
Δ V (change in volume in system) = Vfinal– Vinitial

Enthalpy Change
At constant pressure, change in enthalpy (ΔH) is expressed as:

Δ H = (E + PV)
=ΔE+PΔV (constant pressure)

where; ΔE means change in internal energy


ΔV means change in volume

Since ΔE = q +w, and


w =P Δ V(at constant pressure), another equation is:

ΔH = ΔE + P Δ V = (qp + w) – w = qp

where; qp means constant pressure

Thus, enthalpy change = heat absorbed or lost at constant pressure.

Positive ΔH means that heat is absorbed by the system from its surroundings
(endothermic), while negative ΔH means that heat is lost from the system
into its surroundings (exothermic).

Enthalpies of Reaction
Enthalpy of reaction (heat of reaction) is defined as the enthalpy change in
a reaction; usually expressed as ΔHrxn.
Since, ΔH = Hfinal– Hinitial

Then enthalpy change is expressed as:


ΔH = Hproducts- Hreactants
General Chemistry
13
Gases and Thermochemistry

Calorimetry
Calorimetry measures enthalpy change or heat flow in a chemical reaction.
A devices used to measure is referred to as calorimeter. Calorimeter
measures the magnitude of the change in temperature in a chemical process.

Heat Capacity and Specific Heat


The heat capacity (C) of an object is the amount of heat needed to raise its
temperature by 1K or 1°C.

Molar heat capacity (Cm) is the amount of heat needed to raise the
temperature of 1 mole of a substance by 1K or 1°C.

The specific heat (Cs) is the amount of heat needed to raise the temperature
of 1gram of the substance by 1K or 1°C. Specific heat is expressed as:

(quantity of heat transferred)


Specific heat = (grams of substance) x (temperature change)

𝑞
𝐶𝑠 = 𝑚 𝑋 ∆𝑇

Change in enthalpy or heat flow can be measured by:


1. Constant-pressure calorimeter – provides measurement of ΔH
directly, reaction is being performed in a constant pressure of the
atmosphere
2. Bomb calorimeter (Constant-volume calorimeter) – useful in
measuring combustion reactions, wherein, reaction between
compounds and excess oxygen occurs.

Figure 9.Coffee cup calorimeter (constant-pressure calorimeter);


https://www.learner.org/courses/chemistry/images/lrg_img/CoffeeCalorimeter.jpg; April 26, 2017

Course Module
Figure 10.Bomb calorimeter;
http://hrsbstaff.ednet.ns.ca/benoitn/chem12/thermochemistry/calorimeter/bomb_calorimeter.htm;
April 26, 2017

Glossary
absolute temperature: expressed in Kelvin (K); 0 K is the lowest
temperature which can be reached
atmospheric pressure: pressure exerted by Earth’s atmosphere which
depends on temperature, location and weather conditions
calorie (cal): amount of energy needed in order to raise the temperature of
1 g of water by 1°C
compressible:able to mix in all proportions
directly proportional: as one amount increases, the other amount
increases, and vice versa
enthalpy: sum of the internal energy and product of pressure and volume in
a system
heat: energy used to cause the temperature of an object to increase
inversely proportional: as one amount increases, the other amount
decreases, and vice versa
internal energy (E): energy possessed by a system; sum of all the kinetic
and potential energy of a system
Joule (J): SI unit of energy
kinetic energy: energy of motion
moles: measurement of atoms and molecules used by chemists
negligible: unimportant; insignificant
General Chemistry
15
Gases and Thermochemistry

partial pressure: amount of pressure exerted by each component gas in a


mixture, independent of the pressure exerted by other gases
potential energy: stored energy
pressure: effect of a force applied to a surface
vapor: gaseous state appearance of solids or liquids
work: energy used to move an object against a force

References and Supplementary Materials

Books and Journals


Brown, T.L., LeMay Jr., H.E., Bursten, B.E., Murphy, C.J., Woodward, P.M.,
Stoltzfus, MW; 2015; Chemistry – The Central Science (13th Edition); Upper
Saddle River, NJ; Pearson Education, Inc.

Chang, R.; 2010; Chemistry (10th Edition); New York; McGraw-Hill


Companies, Inc

Online Supplementary Reading Materials


Properties of Gases; http://www.chem1.com/acad/webtext/gas/; April 27,
2017

Understanding Entropy;
http://www.chem1.com/acad/webtut/thermo/entropy.html; April 27, 2017

Basic Thermochemistry;
http://physics.unm.edu/Courses/Duncan/physics452/048/EvansL2.pdf;
April 27, 2017

Thermochemistry;
http://www.oneonta.edu/faculty/viningwj/chem111/chapter_05_4_sy.pdf;
April 27, 2017

Thermochemistry;
https://ww2.odu.edu/~ppleban/pdf/chem115/Zumdahl6.pdf; April 27,
2017

Course Module
Online Instructional Videos
The Ideal Gas Law;
https://www.youtube.com/watch?v=BxUS1K7xu30&index=12&list=PL8dPu
uaLjXtPHzzYuWy6fYEaX9mQQ8oGr; April 26, 2017

The Ideal Gas Problems;


https://www.youtube.com/watch?v=8SRAkXMu3d0&index=13&list=PL8dP
uuaLjXtPHzzYuWy6fYEaX9mQQ8oGr; April 26, 2017

Partial Pressures & Vapor


Pressure;https://www.youtube.com/watch?v=JbqtqCunYzA&index=15&list=
PL8dPuuaLjXtPHzzYuWy6fYEaX9mQQ8oGr&spfreload=5; April 26, 2017

Passing Gases: Effusion, Diffusion and the Velocity of a Gas;


https://www.youtube.com/watch?v=TLRZAFU_9Kg&index=16&list=PL8dPu
uaLjXtPHzzYuWy6fYEaX9mQQ8oGr; April 26, 2017

Energy & Chemistry;


https://www.youtube.com/watch?v=GqtUWyDR1fg&index=17&list=PL8dPu
uaLjXtPHzzYuWy6fYEaX9mQQ8oGr; April 26, 2017

Enthalpy;https://www.youtube.com/watch?v=SV7U4yAXL5I&list=PL8dPuu
aLjXtPHzzYuWy6fYEaX9mQQ8oGr&index=18; April 26, 2017

Calorimetry;https://www.youtube.com/watch?v=JuWtBR-
rDQk&index=19&list=PL8dPuuaLjXtPHzzYuWy6fYEaX9mQQ8oGr; April 26,
2017

Entropy: Embrace the


Chaos!;https://www.youtube.com/watch?v=ZsY4WcQOrfk&index=20&list=
PL8dPuuaLjXtPHzzYuWy6fYEaX9mQQ8oGr; April 26, 2017

First Law of Thermodynamics;


https://www.youtube.com/watch?v=Xb05CaG7TsQ&list=PL1A79AF620ABA
411C&index=67; April 26, 2017