PHASE DIAGRAMS OF ONE COMPONENT SYSTEMS

PHASE DIAGRAM OF WATER PHASE DIAGRAM OF CARBON DIOXIDE PHASE DIAGRAM OF SULPHUR

PHASE DIAGRAM OF WATER

WATER is the most common e.g. of 1 C System It can exists in 3 Phases (Ice, water, vapor) Composition of each phase can be specified in terms of water Different phases of water can exist under different conditions of T & P

Salient characteristics of phase diagram of water

CURVE OA Represents equilibrium between liquid water & vapor at different Temperatures Water Vapor

So on curve OA, P=2, C=1 Applying phase rule F= C-P+2 = 1-2+2 = 1 Hence the curve OA is univariant. Curve OA is called vaporization curve or vapor pressure curve as it gives vapor pressure of water at different temperatures

Salient characteristics of phase diagram of water

At 100 C, the vapor press. of water is equal to atmos. press i.e. 1 atm or 760 mm of Hg. So 100 C is the BP of water Curve OA starts from point O, which is the triple point of water (0.0098 C, 4.58 mm) and ends at point A which corresponds to Tc and Pc (374 C, 218 atm) Beyond this temp, water in liq. Form can not exist.

Salient characteristics of phase diagram of water

Consider a point P on the curve OA. At this point P, liq water and vapor are in eqil. If T is increased along line PX, by keeping P constant, then liq phase will disappear. Similarly if P is decreased along line PN by keeping T constant, then liquid phase will disappear. Hence, in the region towards right side of point P, only vapor phase can exist

Salient characteristics of phase diagram of water

Similarly, if T is decreased along line PY by keeping pressure constant, or if P is increased along line PM by keeping T constant, then vapor phase will disappear Thus, in the region towards left side of point P i.e. in AOC region, only liquid phase can exist CURVE OB The curve OB represents eqil. Between ice & vapor Ice Vapor So, on curve OB, P=2, C=1 Hence F=C=P+2= 1-2+2=1 So, Curve OB is univariant Curve OB is called sublimation curve. Curve OB starts from point O and extends upto point B (-273C)

Salient characteristics of phase diagram of water

CURVE OC The curve OC represents eqil. Between ice & vapor Ice Water

So, on curve OC, P=2, C=1 Hence F=C-P+2= 1-2+2=1 So, Curve OC is univariant Curve OC is called fusion curve. It shows effect of press. On melting point of ice. As can be seen from the diagram, curve OC is inclined towards pressure axis. This indicates that melting point of ice decreases as pressure increases.

Salient characteristics of phase diagram of water

Regions between curves
The curves OA, OB, OC are dividing the phase diagram in three regions or areas i.e. Area AOC, BOC and AOB. In each of these areas only 1 phase is +nt. The region bounded by 2 curves give the conditions of T & P under which a single phase can exist. AOC Represents water, BOC Represents ICE & AOB Represents vapor phase

Salient characteristics of phase diagram of water

In all these areas (AOC, BOC, AOB) P=1 (WATER or ICE or VAPOR) C=1 (WATER) Applying phase rule F=CP+2 =11+2=2

So the degrees of freedom in these areas is 2 (i.e system is bivariant) as both T & P are required to be fixed to specify the state of system.

Salient characteristics of phase diagram of water Triple Point (O)

Where the curves OA, OB & OC meet is called triple point. At triple point, T is 0.0098C and P is 4.58 mm 3 phases can co-exist at this point Ice Water Vapor So at Triple point P=3 (WATER,ICE, VAPOR) C=1 (WATER) Applying phase rule F = C P + 2 = 1 3 + 2 = 0 (invariant) as both T & P are fixed

Salient characteristics of phase diagram of water

Meta stable curve (OA')
When T is decreased at point A, water gets transformed into ice and curve OB is obtained.
If water present at point O is carefully and slowly cooled then it is possible to take water below its normal freezing point without the formation of ice and the curve OA' is obtained which corresponds to super cooled water

The curve OA represents the following eqil. Water Vapor

Super cooled

This eqil. is called metastable eqilibrium because even a small disturbance in the system will convert super cooled water into ice and curve OA will be merged into OB

Values of T & P in some cases of water

Freezing Point of water
- 0C, 1 atm

Boiling Point of water

- 100C, 1 atm

Triple Point of water

- 0.0098C, 4.58 mm

Melting Point of water

- 0C, 1 atm

WATER VAPOUR Clausius-Clapeyron equation Humidity variables Clausius-Clapeyron Equation We wish to determine the equilibrium pressure along the three phase-equilibrium curves (see last figure). As an example of the method, consider the liquid-vapour equilibrium sketched below:

Benoit-Pierre-Emile Clapeyron (1799-1864) was a French civil engineer who worked on the design and construction of steam engines. He is best known for the equation describing the equilibrium vapour pressure over a liquid. The equation was ignored until Clausius and Kelvin revealed its true significance for thermodynamics.

A projection of this surface onto the p-T plane is shown in the accompanying diagram:

Note the supercooled water-vapour equilibrium which is not shown on the 3D thermodynamic surface. The following data, relating to this phase diagram, may be useful: LATENT HEATS lv=2.501106 Jkg-1 lf=0.334106 Jkg-1 ls=2.835106 Jkg-1

Note that ls=lv+lf and that the latent heats are functions of temperature (Kirchoffs law). (v=vapourization, f=fusion, s=sublimation)