03 Chapter 13 Entropy

GENERAL
P R I N C I P L E SCHEMISTRY
AND MODERN
A P P L I C AT I O N S
ELEVENTH EDITION
PETRUCCI HERRING MADURA BISSONNETTE
Spontaneous Change:
Entropy and Gibbs Energy 13
PHILIP DUTTON
UNIVERSITY OF WINDSOR
DEPARTMENT OF CHEMISTRY AND BIOCHEMISTRY
Slide 13 - 1 General Chemistry: Chapter 13 Copyright © 2017 Pearson Canada Inc.

CONTENTS
Spontaneous Change:
Entropy and Gibbs 13-1 Spontaneity: The Meaning of
Spontaneous Change
Energy 13-2 The Concept of Entropy
13-3 Evaluating Entropy and entropy
Changes
13-4 Criteria for Spontaneous Change: The
Second Law of Thermodynamics
13-5 Standard Gibbs Energy Change, ΔG
13-6 Gibbs Energy Change and

Equilibrium
13-7 ΔG° and K as Functions of
Temperature
13-8 Coupled Reactions

The melting of an ice cube occurs spontaneously at temperatures above 0°C

Potential energy decreases.
For chemical systems the internal energy U is equivalent to
potential energy.
Berthelot and Thomsen 1870’s.

Spontaneous change occurs in the direction in which the enthalpy of
a system decreases.
Mainly true but there are exceptions.
Ba(OH)2 . 8 H O - NH Cl
2 4
Slide 4 of 43 General Chemistry: Chapter 19 Copyright © 2011 Pearson Canada Inc.

FIGURE 13-2
Expansion of an ideal gas into a vacuum

6-7 Kinetic Molecular Theory of Gases
• Particles are point masses in constant,

random, straight line motion.
• Particles are separated by great

distances.
• Collisions are rapid and elastic.
• No force between particles.
• Total energy remains constant.
Figure 6-14
Visualizing Molecular Motion

19-2 The Concept of Entropy
Random motion of the gas

particles readily explains
why the gas occupies the
whole volume after a
short time.
There is no enthalpy
change in the process as
there was vacuum in the
right bulb.
Genius of Disorder
FIGURE 19-1
Expansion of an ideal gas into a vacuum Genius of Disorder
If a gas expands against an external pressure, work
is done by the
gas
w=Fxd
= (m x g) x h
(m x g)
=  h x A
A
= PV
w = -PextV
FIGURE 7-8
Pressure-volume work

6-2 Simple Gas Laws
P2 and P1 represent the

internal pressure
(which is always equal
to the external
pressure used to
compress the gas)
1 PV = constant
Pa
V at constant T
Figure 6-6
Relationship between gas volume and pressure – Boyle’s Law

Path Dependent Functions
w = – (1.80 atm)(1.3590-1.0188)L –
(1.20 atm)(2.0377-1.3590)L
= – 0.61236 L atm – 0.81444 L atm

= – 1.4268 L atm x 101.32 J / L atm
= – 1.45 x 102 J
Compared – 1.24  102 J

for the one stage process
FIGURE 7-11
A two-step expansion for the gas shown in Figure 7-8

Reversible process
infinitesimal changes in a
system variable
Irreversible process
stepwise processes are
irreversible
FIGURE 7-12
A different method of achieving the expansion of a gas

Irreversible process:
6-2 Simple Gas Laws Taking one weight off and
expanding against constant
external pressure P1:
wirrev = - P1 DV
wirrev
1
Pa
V
Figure 6-6

wirrev = - P1 DV
1
Pa
V
Figure 6-6

wirrev = - P1 DV
w wrev > wirrev

rev
1
Pa
V 𝑉 𝑓
𝑤 𝑟𝑒𝑣=− ∫ 𝑃 𝑑𝑉
Figure 6-6 𝑉𝑖

Reversible processes
If the steps are made smaller and smaller, the work

becomes larger up to an optimal value.
The process can be reversed to reach the original

initial state.
05/07/2023Copyright © 2011 Pearson

Slide 15 of 57 General Chemistry: Chapter 7 Canada Inc.
The First Law of Thermodynamics
A system contains only internal energy.

A system does not contain heat or work.
These only occur during a change in the system.
U = q + w
Law of Conservation of Energy

The energy of an isolated system is constant

7-5 The First Law of Thermodynamics
Internal Energy, U.
Total energy (potential and
kinetic) in a system.
• Translational kinetic energy.

• Molecular rotation.
• Bond vibration.
• Intermolecular attractions.
• Chemical bonds.
• Electrons.
FIGURE 7-9
Some contributions to the internal energy of a system

The Kinetic-Molecular Theory
Kinetic energy
Ekin = 1/2 m u2
For one mole of ideal gas
Ekin = 1/2 NO m u2 = 3/2 1/3 NO m u2
Ekin = 3/2 R T
The average kinetic energy of an ideal gas depends only

on the temperature
Ekin is independent of mass and density
Oxtoby, Nachtrieb, Modern Chemistry 3rd Edition

VaT V=bT
Figure 6-7
Gas volume as a function of temperature

If a gas is expanded against a pressure and heat is not
supplied, it6-7gets colder and its final volume is smaller.
Figure
Gas volume as a function of temperature

Carnot Cycle:
Irreversible process Reversible process
𝑉 𝑓
𝑤 𝑖𝑟𝑟𝑒𝑣=− 𝑃𝑓 ∆ 𝑉 𝑤 𝑟𝑒𝑣=− ∫ 𝑃 𝑑𝑉
𝑉𝑖
𝑛 𝑅𝑇
𝑃=
𝑉
𝑉 𝑓 𝑉 𝑓
𝑛 𝑅𝑇 1
𝑤 𝑟𝑒𝑣=− ∫ 𝑉
𝑑𝑉 =− 𝑛 𝑅 𝑇 ∫ 𝑉
𝑑𝑉 = ¿ ¿
𝑉𝑖 𝑉 𝑖
¿ − ¿
Isothermal: =

Changing T stepwise
dS = dqrev / T (T= const = T before q is supplied) (13.2)
If isothermal:

Statistical Interpretation

Richard Feynman
1918-1988
Nobel Prize 1965

If, in some cataclysm, all of scientific knowledge were to be
destroyed, and only one sentence passed on to the next
generations of creatures, what statement would contain the
most information in the fewest words?
I believe it is the atomic hypothesis (or the atomic fact, or

whatever you wish to call it):
All things are made of atoms—little particles that

move around in perpetual motion, attracting each
other when they are a little distance apart, but
repelling upon being squeezed into one another.
Slide 25 of 27
http://www.feynmanlectures.caltech.edu/I_01.html#Ch1-S1
13-1 Entropy: Boltzmann’s View
Microstates
Macroscopic systems are made up of many particles.

System is easily characterized (n, T, V, P)
Microscopic systems are not easily characterized.
Positions, velocity and energy of individual molecules change
from one instant to the next.
According to quantum mechanics a microstate is a specific
microscopic configuration describing how the particles of a
system are distributed among the available energy levels.

Gerd Wedler, Lehrbuch der Physikalischen Chemie
En = n2h2/8mL2
FIGURE 13-1
Enumeration of microstates

• When the space available to the particles of a system is fixed,
W and S increase as the total energy, U, increases or as T
increases.
• When the total energy of a system is fixed, W and S increase
as the space available to the particles increases

The Boltzmann Equation for Entropy
S = kB lnW
Entropy, S, is a thermodynamic property related to the way
in which the energy of a system is distributed among the
available energy levels.
States.
The microscopic energy levels available in a system.
Microstates, W.
The particular way in which particles are distributed amongst the
states. Number of microstates = W.
The Boltzmann constant, kB.

Effectively the gas constant per molecule kB = R/NO (or R/NA).

Probability p that a system has a given energy
Quantized version: number of Ni particles with energy Ei
Example: T = 25 ºC, how many particles in a mole have

an energy of 10 kJ/mol?
kb T = 1.3807 x 10-23 J/K x 298.15 K = 4.1165 x 10-21 J
R T = kb T NA = 2.479 kJ/mol
NiNA = x 6.0221 x1023 mol-1 =
= 0.017705 x 6.0221 1023 mol-1 = 1.07 x 1022 mol-1

Isothermal:
H = U + PV
DH = DU + D(PV)
U = 3/2 RT
FIGURE 13-2

Isothermal:
H = U + PV
DH = DU + D(PV)
DU = 0
Pressure halves, volume doubles

D(PV) = 0
DH = 0
Vf > Vi, Wf > Wi
FIGURE 13-2
DS increases
Microscopic Interpretation of Entropy Change
Mixing is spontaneous,
although there is no
energy change as ideal
gas particles do not
interact.
The gases mix because

the entropy increases.
Each gas in the

mixtures has more
accessible microstates.
FIGURE 13-3
The mixing of ideal gases

A(g) + B(g) mixture of A(g) and B(g)
∆S = kB ln Wf – kB ln Wi = kB( ln Wf – ln Wi) > 0

Describing Entropy Change
for Some Simple Processes
FIGURE 13-4
Three processes in which entropy increases

Four situations generally produce an increase in entropy:
• Pure liquids or liquid solutions are formed from solids.
• Gases are formed from either solids or liquids.
• The number of molecules of gas increases as a result of a chemical reaction.
• The temperature of a substance increases.

Predict whether each of the following processes involves
an increase or a decrease in entropy or whether the
outcome is uncertain.
(a) The decomposition of ammonium nitrate (a fertilizer

and a highly explosive compound)
(b) The conversion of (a key step in the manufacture of
sulfuric acid)
(c) The extraction of sucrose from cane sugar juice.
(d) The “water gas shift” reaction (involved in the
gasification of coal)

PRACTICE EXAMPLE B: Predict whether entropy
increases or decreases or whether the outcome is
uncertain in each of the following reactions.

Reversible Heat Transfer
dS = dqrev / T (T= T before q is supplied) (13.2)
Finite entropy change
If isothermal:

Phase transitions
(happen naturally at const. T)
For any transition:

ΔHtr
ΔStr = (13.3)
Ttr
H2O(s, 1 atm) H2O(l, 1 atm) ΔfusH° = 6.02 kJ at 273.15 K
ΔfusH ° 6.02 kJ mol−1

Δ fusS = = = 22.0 J mol −1 K −1
Tmp 273.15 K
Trouton’s Rule: For many liquids at their boiling points,
ΔvapH°
ΔvapS = ≈ 87 J mol −1 K −1 (13.4)
Tbp

The entropy change for the transition from solid
rhombic sulfur to solid monoclinic
sulfur at 95.5 C is
What is the standard molar enthalpy change,

for this transition?

Heating or Cooling at Constant Pressure
dS = qrev/T
dS = (Cp/T) dT
Assumption: Cp is same for all T

Changes in State for an Ideal Gas

Example: Calculate the entropy change for the
following constant pressure process.
The molar heat capacities of ice and water are,

respectively, = 37.12 J/mol K and = 75.3 J/mol K .
The enthalpy of fusion for ice is 6.01 kJ/mol
at 0 C.

PRACTICE EXAMPLE A: One mole of neon gas, initially at
300 K and 1.00 bar, expands adiabatically (i.e., with no
heat lost to the surroundings) against a constant external
pressure of 0.50 bar until the gas pressure is also
0.50 bar. The final temperature of the gas is 240 K. What is
DS for the gas? The molar heat capacity of Ne(g) is
20.8 J/mol K .

13-3 Combining Boltzmann’s and Clausius’s
Ideas: Absolute Entropies
Third law of thermodynamics
The entropy of a pure perfect crystal at 0 K is zero.
Standard molar entropy, Sº

Tabulated in Appendix D.
ΔS = [ ∆pSº(products) − ∆rSº (reactants)]

FIGURE 13-5
Molar entropy as a function of temperature

Standard molar entropy, Sº
Tabulated in Appendix D.

Standard molar entropy, Sº, increases as molecular complexity increases (i.e., as
the number of atoms per molecule increases).
FIGURE 13-6
Vibrational energy and entropy

13-4 Criterion for Spontaneous Change:
The Second Law of Thermodynamics.
ΔSuniverse = ΔSsystem + ΔSsurroundings > 0 (13.10)
All spontaneous processes produce an increase in the entropy of

the universe.

Ideas about entropy can be summarized as follows.
ΔSuniv > 0, the process is spontaneous.

ΔSuniv < 0, the process is nonspontaneous.
ΔSuniv = 0, the process is reversible.

Supercooled water at -10 ºC
Water freezes spontaneously at -10 ºC but it can not be done

reversibly. As entropy is a state function, the process can be done
in steps. Warming slowly to the normal melting point of 0 ºC ,
freezing slowly, cooling slowly.
irreversible
reversible

K-1

K-1

K-1

= 5630 J / 263.15 K = 21.4 J K-1
DSuniv = DSsys + DSsurr = -20.6 J K-1 + 21.4 J K-1 = 0.8 J K-1 > 0

= 5630 J / 263.15 K = 21.4 J K-1

= 5630 J / 263.15 K = 21.4 J K-1

= 5630 J / 263.15 K = 21.4 J K-1

The entropy change of the system is negative, nonetheless
water freezes. Why?

The entropy change of the system is negative, nonetheless
water freezes. Why?

To determine whether a process occurs the entropy of
system and surroundings must be considered.
The entropy of the surrounding increases because freezing

is exothermic and the heat is given to the surroundings.
= 5630 J / 263.15 K = 21.4 J K-1

Gibbs Energy and Gibbs Energy Change
Hypothetical process:
only pressure-volume work, at constant T and P.
qsurr = – qp = – ΔHsys
Make the enthalpy change reversible.

large surroundings, infinitesimal change in temperature.
Under these conditions we can calculate entropy.
DSsurr = – ΔHsys / T
TDSsurr = – ΔHsys

DSuniv = DSsys + DSsurr
TDSuniv = TDSsys + TDSsurr
For the universe:

TΔSuniv = TΔSsys – ΔHsys
–TΔSuniv = ΔHsys – TΔSsys
For the system:

G = H – TS (13.12)
ΔG = ΔH – TΔS (13.13)
ΔGsys = –TΔSuniv.

Criteria for Spontaneous Change
ΔGsys < 0 (negative) the process is spontaneous.
ΔGsys > 0 (positive) the process is nonspontaneous.
ΔGsys = 0 (zero) the process is at reversible and the system has

reached equilibrium.
J. Willard Gibbs (1839–1903)

—a great “unknown” scientist

Applying the Gibbs Energy Criteria for
Spontaneous Change

PRACTICE EXAMPLE A: Which of the four
cases in Table 13.3 would apply to each of
the following reactions?

13-5 Gibbs Energy Change of a System of
Variable Composition: ΔrGº and ΔrG
Pure, unmixed reactants Pure, unmixed products
(each in its standard state) (each in its standard state)
aA + bB + … cC + dD + …

The standard free energy of formation, ΔfGº.
The change in free energy for a reaction in which a substance in its
standard state is formed from its elements in reference forms in their
standard states.
The standard free energy of reaction, ΔGº.
ΔrGº = Δ r Hº – T r ΔSº
ΔrGº = [∑ ΔfGº (products) − ∑ΔfGº (reactants)] (13.14)

End of Chapter

At 298.15 K, the heat of formation of liquid pentane is -173.5
kJ/mol, the heat of formation of gaseous pentane is -146.9
kJ/mol. What is the normal boiling point of pentane?

Gibbs Energy and Work
The second law guarantees that
∆G ≤ wnon-PV
if wnon-PV = 0, then ∆G ≤ 0
Considering sign conventions

( w > 0 when work is done on the system, w < 0 when work is
done by the system)
wnon-PV = – | wnon-PV | when the system does non-PV work
| wnon-PV | ≤ –∆G

Gibbs Energy of Reaction for Nonstandard
Conditions, ΔrG

FIGURE 13-8
Variation of G at constant T and constant P

1. If ∆rG < 0, then G decreases as ξ increases.
2. If ∆rG > 0, then G increases as ξ increases.
3. If ∆rG = 0, then the system has attained the

minimum possible value of G.

The Thermodynamic Reaction Quotient, Q
N2(g) + 3 H2(g) 2 NH3(g)

aA + bB + … cC + dD + …
(13.16)

Relationship of ΔrGº to
the Equilibrium Constant K
If the reaction is at equilibrium then:
0 = Δ r G° + RT ln Qeq = Δ r G° + RT ln K
Δ r G° = –RT ln K (13.17)
If the reaction is not at equilibrium then:

Δ r G = Δ r G° + RT ln Q = –RT ln K + RT ln Q
(13.18)
Δ r G = RT ln(Q/K)
we can predict the direction of spontaneous change

Δ r G = RT ln(Q/K) (13.18)

Different Forms of the Equilibrium Constant
aA + bB + … cC + dD + …
(13.19)

For reactions involving gases
define (13.20)
(13.21)

In aqueous solutions
(13.22)
(13.23)

In heterogeneous solutions
2 Al(s) + 6 H+(aq) 2 Al3+(aq) + 3 H2(g)

Interpreting the values of ∆rGº and K
Δ r Gº = –RT ln K (13.17)

Consider the implications on the position of
the equilibrium for large or small values of K.
Without loss of generality, we can think about a

gas phase equilibrium
aA(g) + bB(g) + … cC(g) + dD(g) + …

FIGURE 13-19
The position of equilibrium for small, large, and intermediate values of K

13-6 ΔrGº and K as Functions of Temperature
ΔrGº = ΔHº–TΔSº Δ r Gº = –RT ln Keq
–ΔGº –ΔHº TΔSº

ln Keq = = +
RT RT RT
–ΔHº ΔSº
ln K = + (13.24)
RT R

2 SO2(g) O2(g) 2 SO3(g)
–ΔHº ΔSº
ln Keq = +
RT R
–ΔHº
slope =
R
–ΔHº = R×slope
= –8.3145 J mol −1 K −1×2.2×104 K
= –1.8×102 kJ mol −1
FIGURE 13-12
Temperature dependence of the equilibrium constant K for the reaction
2 SO2(g)+O2(g) 2 SO3(g)
Van’t Hoff Equation
–ΔHº ΔSº
evaluate ln K = + for a change in temperature:
RT R
K2 –ΔHº ΔSº –ΔHº ΔSº

ln = + – +
K1 RT2 R RT1 R
K2 –ΔHº 1 1
ln = – (13.25)
K1 R T2 T1
13-7 Coupled Reactions
In order to drive a non-spontaneous reactions we changed the
conditions
(i.e. temperature or electrolysis).
Another method is to couple two reactions.

One with a positive ΔG and one with a negative ΔG.
Overall spontaneous process.
Smelting Copper Ore
Cu2O(s)Δ 2 Cu(s) + ½ O2(g) ΔGº673K = +125 kJ mol–1
Non-spontaneous reaction: Cu2O(s) 2 Cu(s) + ½ O2(g) +125 kJ mol–1
Spontaneous reaction: C(s) + ½ O2(g) CO(g) −175 kJ mol–1
Cu2O(s) + C(s) 2 Cu(s) + CO(g) −50 kJ mol–1
Spontaneous reaction!
13-8 Chemical Potential and Thermodynamics
of Spontaneous Chemical Change
Gibbs Energy of an Ideal Gas
for an isothermal process, ∆H = 0
use Gº and G to represent initial and final states
(13.28)
molar Gibbs energy (13.29)
Gibbs Energy of an Ideal Gas Mixture
(13.30)
If we change the amount of A by ∆nA moles
relates the change in Gibbs energy to the change in amount of gas A

Chemical Potential and Activity
(13.29)
(13.31)
(13.30)
(13.32)
(13.33)
The concept of activity was introduced by Lewis to ensure that
the chemical potential of a substance always has the form
given by equation
(13.31)
It is not particularly helpful

to think of activity as an
effective pressure or an
effective concentration. It is
much better to think of
pressure and concentration
as providing a measure of
activity.
Expressing ∆rGº in Terms of Chemical Potentials
Initial State Initial State
Pure A at 1 bar, nA = a mol Pure C at 1 bar, nC = c mol
Pure B at 1 bar, nB = b mol Pure D at 1 bar, nD = d mol
(13.34)
Weighted sum of µ° Weighted sum of µ°

values for products values for reactants
Criterion for Predicting the Direction
of Spontaneous Chemical Change
dξ > 0
aA + bB cC + dD
dξ < 0
Initial: nA nB nC nD Gi
Change: –a dξ –b dξ +c dξ +d dξ +dG
Final: nA –a dξ nB –b dξ nC +c dξ nD +d dξ Gf = Gi+dG
dG =Gf – Gi
(13.35)
where (13.36)
recall (13.31)
(13.36)
(13.15)

03 Chapter 13 Entropy

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GENERAL

PETRUCCI HERRING MADURA BISSONNETTE

Slide 13 - 1 General Chemistry: Chapter 13 Copyright © 2017 Pearson Canada Inc.

13-5 Standard Gibbs Energy Change, ΔG

13-6 Gibbs Energy Change and

Slide 13 - 2 General Chemistry: Chapter 13 Copyright © 2017 Pearson Canada Inc.

Slide 13 - 3 General Chemistry: Chapter 13 Copyright © 2017 Pearson Canada Inc.

Berthelot and Thomsen 1870’s.

Slide 4 of 43 General Chemistry: Chapter 19 Copyright © 2011 Pearson Canada Inc.

Slide 13 - 5 General Chemistry: Chapter 13 Copyright © 2017 Pearson Canada Inc.

• Particles are point masses in constant,

• Particles are separated by great

• No force between particles.

• Total energy remains constant.

Slide 6 of 41 General Chemistry: Chapter 6 Copyright © 2011 Pearson Canada Inc.

Random motion of the gas

Slide 8 of 57 General Chemistry: Chapter 7 Copyright © 2011 Pearson Canada Inc.

P2 and P1 represent the

Slide 9 of 41 General Chemistry: Chapter 6 Copyright © 2011 Pearson Canada Inc.

= – 0.61236 L atm – 0.81444 L atm

Compared – 1.24  102 J

Slide 10 of 57 General Chemistry: Chapter 7 Copyright © 2011 Pearson Canada Inc.

Slide 7 - 11 General Chemistry: Chapter 7 Copyright © 2017 Pearson Canada Inc.

Slide 12 of 41 General Chemistry: Chapter 6 Copyright © 2011 Pearson Canada Inc.

Slide 13 of 41 General Chemistry: Chapter 6 Copyright © 2011 Pearson Canada Inc.

w wrev > wirrev

Slide 14 of 41 General Chemistry: Chapter 6 Copyright © 2011 Pearson Canada Inc.

If the steps are made smaller and smaller, the work

The process can be reversed to reach the original

05/07/2023Copyright © 2011 Pearson

A system contains only internal energy.

Law of Conservation of Energy

Slide 16 of 57 General Chemistry: Chapter 7 Copyright © 2011 Pearson Canada Inc.

• Translational kinetic energy.

Slide 17 of 57 General Chemistry: Chapter 7 Copyright © 2011 Pearson Canada Inc.

For one mole of ideal gas

Ekin = 1/2 NO m u2 = 3/2 1/3 NO m u2

The average kinetic energy of an ideal gas depends only

Ekin is independent of mass and density

Oxtoby, Nachtrieb, Modern Chemistry 3rd Edition

Slide 19 of 41 General Chemistry: Chapter 6 Copyright © 2011 Pearson Canada Inc.

Slide 20 of 41 General Chemistry: Chapter 6 Copyright © 2011 Pearson Canada Inc.

Slide 13 - 21 General Chemistry: Chapter 13 Copyright © 2017 Pearson Canada Inc.

dS = dqrev / T (T= const = T before q is supplied) (13.2)

Slide 13 - 22 General Chemistry: Chapter 13 Copyright © 2017 Pearson Canada Inc.

Slide 23 of 43 General Chemistry: Chapter 19 Copyright © 2011 Pearson Canada Inc.

Slide 24 of 27 General Chemistry: Chapter 3 Copyright © 2011 Pearson Canada Inc.

I believe it is the atomic hypothesis (or the atomic fact, or

All things are made of atoms—little particles that

Macroscopic systems are made up of many particles.

Slide 13 - 26 General Chemistry: Chapter 13 Copyright © 2017 Pearson Canada Inc.

Slide 13 - 28 General Chemistry: Chapter 13 Copyright © 2017 Pearson Canada Inc.

Slide 13 - 29 General Chemistry: Chapter 13 Copyright © 2017 Pearson Canada Inc.

The Boltzmann constant, kB.

Slide 13 - 30 General Chemistry: Chapter 13 Copyright © 2017 Pearson Canada Inc.

Example: T = 25 ºC, how many particles in a mole have

kb T = 1.3807 x 10-23 J/K x 298.15 K = 4.1165 x 10-21 J

NiNA = x 6.0221 x1023 mol-1 =

= 0.017705 x 6.0221 1023 mol-1 = 1.07 x 1022 mol-1

Slide 13 - 32 General Chemistry: Chapter 13 Copyright © 2017 Pearson Canada Inc.

Pressure halves, volume doubles

Vf > Vi, Wf > Wi

The gases mix because