UNIT 2

PHASE-CHANGE PROCESSES OF PURE SUBSTANCES AND PROPERTY DIAGRAMS

Unit Structure 2.0 2.! 2.2 2.* Overvie "e#rnin$ O%&ective' Intr()ucti(n P+#'e-C+#n$e Pr(ce''e' (, Pure Su%'t#nce' 2.*.! 2.*.2 2.*.* 2.1 2.3 2.4 C(-.re''e) "i/ui)-S#tur#te) "i/ui) S#tur#te) "i/ui)-Su.er+e#te) 0#.(ur S#tur#ti(n Te-.er#ture #n) Pre''ure

Pr(.ert2 Di#$r#-' Su--#r2 An' er' t( Activitie'

2.0

O0ER0IE5

Any pure substance, for example water, can exist in different forms. In the case of water, these forms will be ice, liquid water and vapour water. This unit deals with the different phases of a pure substance, the transformations occurring when it passes from one phase to another and the illustration of these phenomena on diagrams known as property diagrams. A good knowledge of A-level hysical !hemistry and in particular the "olecular Theory of "atter and the #tate of "atter are essential pre-requisites for an appropriate understanding of the unit.

Unit 2

2.!

"EARNING OB6ECTI0ES

%y the end of this unit, you will be able to do the following& $. '. ). Identify the different phases of pure substances. (escribe, in detail, phase changes Illustrate these changes on property diagram.

2.2

INTRODUCTION

A pure substance is one that has a fixed chemical composition throughout. *or example, air, water, nitrogen, helium etc+. are pure substances. A pure substance need not be constituted of only one element. A mixture of liquid water and ice is still considered to be a pure substance because the chemical composition is the same throughout. A substance usually exists in three principal phases& solid, liquid and gaseous. #ome substances might even exist under several forms in the same state, for example diamond and graphite are solid forms of !arbon. A phase is defined as one having a distinct molecular arrangement, which is homogeneous throughout, and which can be differentiated from other phases by clearly distinguishable boundaries.

2.*

PHASE-CHANGE PROCESSES OF PURE SUBSTANCES.

It can be shown from several practical examples that two phases of a pure substance coexist in equilibrium - for example, liquid water and vapour water in the boiler and condenser of a steam power plant. Another example would be the refrigerant in the refrigerator where the liquid and gaseous refrigerant are in equilibrium in the free-er. .e will now consider the phase changes that accompany the transformation of liquid water to

Unit 2

'

vapour water and you should note that all pure substances will exhibit the same general behaviour.

2.*.! C(-.re''e) "i/ui)

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S#tur#te) "i/ui).

!onsider water at '/ ! and under $atm pressure in a piston-cylinder device. 0nder such conditions, water is said to be in the liquid phase and is called compressed liquid or sub-cooled liquid 1i.e. one which is not on the point of vaporising2. St#te !

P 8 ! #t- #n) T 8 200C Fi$ure 2.!7 C(-.re''e) "i/ui) 'If heat is now transferred to the water, the temperature of the water will rise. As the temperature rises, the liquid expands and the specific volume increases slightly. .hen the temperature has reached $// !, the liquid will be in a saturated state. 1i.e. one, which is on the point of vaporising2. St#te 2

P 8 ! #t- #n) T 8 !000C Fi$ure 2.27 S#tur#te) "i/ui)

Unit 2

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If more heat is supplied, the saturated liquid will boil and the temperature remains constant during boiling process. 3ou will note that boiling is accompanied by an increase in volume and a decrease in liquid level. .hen all the liquid has boiled into vapour, we have a saturated vapour. 1i.e. a saturated vapour is one which is about to condense if there is any slight heat loss2. St#te *

P 8 ! #t- #n) T 8 !000C Fi$ure 2.*7 S#tur#te) 0#.(ur '- The supply of heat to a saturated vapour will increase the temperature of the vapour and at around )// !, we will obtain a superheated vapour. 1i.e. one that is not on the point of condensing if there is a slight heat loss2. The volume also increases. St#te 1

P 8 ! #t- #n) T 8 *000C Fi$ure 2.17 Su.er+e#te) 0#.(ur The above processes of phase changes can be represented on a T-v diagram as shown in figure '.4&

Unit 2

Te-. T=0C *00 1

!00 ! 20

S.eci,ic 0(:u-e; v -*=>$ Fi$ure 2.37 T-v Di#$r#- 9P(int !7 C(-.re''e) :i/ui); P(int 27 S#tur#te) :i/ui);
P(int *7 S#tur#te) 0#.(ur; P(int 17 Su.er+e#te) 0#.(ur<

2.*.* S#tur#ti(n Te-.er#ture #n) Pre''ure

The saturation pressure
sat

is the pressure at which a pure substance changes phase at a

given temperature. The saturation temperature Tsat is the temperature at which a pure substance changes phase at a given pressure. It has been shown experimentally that the temperature at which water starts boiling depends on the pressure. *or example, at $/$.) k a 1$ atm2, water will boil at $// ! whereas under 4// k a, water will boil at $4$.6 !.
sat k a

T'#t 0C

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Unit 2

*rom the above curve, it can be deduced that Tsat increases with

sat.

The previous experiment was carried out under a pressure of $ atm. If we now increase the pressure successively, by adding weights on the cylinder until the pressure reaches, say to $ " a, 7 " a, ''./6 " a and '4 " a, we will obtain more or less identical trends for the variation of T and v at each of the pressures and these can be illustrated on the T-v diagram&
T0C 23 MP# 22.0A MP# @ MP# ! MP# ! #t-

v -*=>$

Fi$ure 2.?7 T-v Di#$r#- ,(r t+e .+#'e c+#n$e 9c(-.re''e) :i/ui)-'u.er+e#te) v#.(ur< #t v#ri(u' .re''ure'.

The following differences can be noted& $2 '2 )2 water has a smaller specific volume, v with increasing . Tsat will increase with 52 As
sat

vsat-liq increases while vsat-vap decreases with increasing #aturated 8iquid-9apour line is shorter. is increased further, the saturation lines continue to shorten until a point is

reached where saturated liquid and saturated vapour states are identical. This point is referred to as critical point.

Unit 2

2.1

PROPERTY DIAGRAMS

The behaviour of properties 1ex. T, v2 during phase-change processes are best studied and understood with the help of property diagrams. If we look back at *igure '.; and <oin the saturated liquid points to form the saturated liquid curve and the saturated vapour points to form the saturated vapour line 1refer to dotted line in *igure '.;2, we will obtain the property diagram as shown in *igure '.7&

T0C

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v -*=>$

Fi$ure 2.@

Pr(.ert2 Di#$r#- T-v ,(r Pure Su%'t#nce'

The region under the curve 1dome2 represents the saturated liquid=vapour mixture region. The region on the left-hand side of the saturated liquid line is the compressed liquid state whereas the region on the right-hand side of the saturated vapour line represents the superheated region. At !ritical point, saturated liquid and vapour states are identical. *or water, the critical point is at pressure > ''./6 " a, T > );5.$5 !.

A similar diagram can be obtained if the experiment is repeated to study the variation of 1instead of Temperature2 with specific volume v at a number of constant temperatures&

Unit 2

P=MP#

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Fi$ure 2.A7

Pr(.ert2 Di#$r#- P-v ,(r Pure Su%'t#nce'

Activitie' $2 '2 )2 .hat is the difference between saturated liquid and compressed liquid ? .hat is the difference between saturated vapour and superheated vapour ? A rigid tank contains some liquid water at ;/ !. The rest of the tank is filled with atmospheric air. Is it possible to boil the water in the tank without raising its temperature ?

2.3 SUMMARY
In this unit, pure substances have been defined and the different phases in which a pure substance can exist 1i.e. solids, liquids and gases2 have been highlighted. A detailed example of a phase change from compressed liquid to superheated vapour has then been used to show how to draw the property diagram 1T-v and -v2 for a pure substance. In the next unit, you will be introduced to property tables and learn how to use them for solving problems.

Unit 2

2.4
$2

ANS5ERS TO ACTI0ITIES
A saturated liquid is one, which is on the point of boiling 1i.e. the slightest addition of heat will cause the liquid to boil into a vapour2 whereas a compressed liquid is not one which will boil if the same amount of heat 1as in the previous case2 is supplied.

'2

A saturated vapour is one that will condense into a liquid if a slight amount of heat is lost or removed. A superheated vapour will not condense into a liquid if the same amount of heat 1as in the previous case2 is lost or removed.

)2

3es, it is possible. The saturation temperature is a function of the saturation pressure and thus by decreasing the pressure, we can lower the saturation temperature. *or example, working in an elevated location can decrease the pressure.

Unit 2