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2014 IPhO Solution To Theory Problem 2

The document discusses the van der Waals equation of state for non-ideal gases and its application to water. It derives formulas for the van der Waals constants a and b in terms of critical temperature and pressure. It also discusses properties of the gas and liquid phases near the critical point, including calculations of minimum gas volume, heat of vaporization, surface tension, and minimum size of stable liquid droplets formed through condensation.

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141 views3 pages

2014 IPhO Solution To Theory Problem 2

The document discusses the van der Waals equation of state for non-ideal gases and its application to water. It derives formulas for the van der Waals constants a and b in terms of critical temperature and pressure. It also discusses properties of the gas and liquid phases near the critical point, including calculations of minimum gas volume, heat of vaporization, surface tension, and minimum size of stable liquid droplets formed through condensation.

Uploaded by

Souseiseki Chrome
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
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Theoretical competition.

Tuesday, 15 July 2014

1/3

Problem 2.Van der Waals equation of state


Solution
Part . Non-ideal gas equation of state
A1.If = is substituted into the equation of state, then the gas pressure turns infinite. It is obvious that this
is the moment when all the molecules are tightly packed. Therefore, the parameter is approximately equal
to the volume of all molecules, i.e.
= 3
(A1.1)
A2.In the most general case thevan der Waals equation of state can be rewritten as
3 + 2 + = 0
(A2.1).
Since at the critical values of the gas parameters the straight line disappears, then, the solution of
(A2.1) must have one real triple root, i.e. it can be rewritten as follows
( )3 = 0
(A2.2).
Comparing the coefficients of expression (A2.1) and (A2.2), the following set of equations is
obtained
3 = +
3 2 =
(A2.3).
3
=
Solution to the set (A2.3) is the following formulas for the van der Waals coefficients
=

27 2 2

(A2.4),

64

= 8

(A2.5).

Alternative solution
The critical parameters are achieved in the presence of an inflection point in the isotherm, at which
the first and second derivatives are both zero. Therefore, they are defined by thefollowingconditions

=0
(A2.6),

and
2

=0

(A2.7).

Thus, the following set of equations is obtained

2
2 + 3 = 0

2
3

6
4

=0

(A2.8),

which has the same solution (A2.4) and (A2.5).


A3.Numericalcalculationsforwaterproduce the following result
= 0.56

m6 Pa

(A3.1).

mole2
m3
3.1 105 mole

=
A4.From equations (A1.4) and (A3.2) it is found that
=

= 3.7 1010 m 4 1010 m

(A3.2).
(A4.1).

Part B. Properties of gas and liquid


B1.Usingtheinequality , the van der Waals equation of state can be written as
0 +

(B1.1),

which has the following solutions

= 2

1 1

40
2 2

(B1.2).

Theoretical competition. Tuesday, 15 July 2014

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Smaller root in (B1.2) gives the volume in an unstable state on the rising branch of thevan der Waals
isotherm. The volume of gas is given by the larger root, since at = 0an expression for the volume of an
ideal gasshould be obtained, i.e.

= 2

1+ 1

40

(B1.3).

2 2

For given values of the parameters the value 02 = 5.8 103 . It can therefore be assumed

that 02 1, then (B1.3)takes the form

2 2

(B1.4).

B2. For an ideal gas

0 =

(B2.1),

hence,

0
0

=2 1 1

40
2 2

0
2 2

= 0.58%.

B3.Mechanical stability of a thermodynamic system is inpower provided that

< 0.

(B2.2)
(B3.1)

The minimum volume, in which the mattercan still exist in the gaseous state, corresponds to a point
in which

= 0
(B3.2).

Using the van der Waals equation of state (B3.2) is written as

2
=
2+ 3 = 0

()

(B3.3).

From (B3.2) and (B3.3), and with the help of , it is found that
2
=
Thus,

2 2

(B3.4).

= 2 = 86

(B3.5).

B4. Usingtheinequality / , the van der Waals equation of state is written as

2 = ,

(B4.1)

whose solution is

= 2 1 1

(B4.2).

In this case, the smaller root shouldbe taken, since at 0the liquid volume = must be obtained
according to (B4.1), i.e.

= 2 1 1

1+

(B4.3).

B5. Since (B4.3) givesthevolumeoftheonemoleofwaterits mass density is easily found as

2 kg
= =
= 5.8 10 m3

(B5.1).

B6. Inaccordancewith (B4.3) the volume thermal expansion coefficient is derived as


1

= = + = 4.6 104 1

(B6.1).

1+

B7.The heat, required to convert the liquid to gas, is used to overcome the intermolecular forces that create
negative pressure / 2 , therefore,

1
1
= 2 =
(B7.1),

and using , (B7.1) yields

= =

1+

= 1.0 106 kg

(B7.2).

Theoretical competition. Tuesday, 15 July 2014

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B8.Consider some water of volume. To make a monolayer of thickness out of it, the following work
must be done
= 2
(B8.1).
Fabrication of the monomolecular layer may be interpreted as the evaporation of an equivalent
volume of water which requires the following amount of heat
=
(B8.2),
where the mass is given by
=
(B8.3).
Using (A4.1a), (B5.1)and(B7.2), one finally gets

N
= 2 2 = 0.12 102 m
(B8.4).

Part . Liquid-gas systems


C1.At equilibrium, the pressure in the liquid and gas should be equalat all depths. The pressurein the fluid
at the depth is related to the pressure of saturated vapor above the flat surface by
= 0 +
(C1.1).
The surface tension creates additional pressure defined by the Laplace formula as
2
=
(C1.2).
The same pressureinthefluidatthedepth depends on the vapor pressure over the curved liquid
surface and its radiusofcurvature as
2
= +
(C1.3).
Furthermore, the vapor pressure at different heights are related by
= 0 +
(C1.4).
Solving (C1.1)-(C1.4), it is found that
2
= ( )
(C1.5).

Hence,the pressure difference sought is obtained as


2
2
= 0 = =
.

(C1.6).

Note that the vapor pressure over the convex surface of the liquid is larger than the pressure above
the flat surface.
C2.Let be vapor pressure at a temperature , and be vapor pressure at a temperature .
In accordance with equation (3) from problem statement, whentheambient temperature falls by an amount of
the saturated vapor pressure changes by an amount

= 2
(C2.1).

In accordance with the Thomson formula obtained in part C1, the pressure of saturated vapor above
the droplet increases by the amountof . While a droplet is small in size, the vapor above its surface
remains unsaturated. Whena droplet hasgrownuptoacertainminimumsize, thevaporaboveitssurface turns
saturated.
Since the pressure remains unchanged, the following condition must hold
+ =
(C2.2).
Assuming the vapor is almost ideal gas, its density can be found as

=
(C2.3).

From equations (C2.1)-(C2.3), (B5.1) and (C1.6) one finds


2

=
2

(C2.4).

Thus, it is finally obtained that


=

2 2

= 1.5 108 m

(C2.5).

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