PHASE DIAGRAMS

TERMINOLOGIES SINGLE COMPONENT PHASE

DIAGRAMS
• PHASE => A SUBSTANCE WHICH IS UNIFORM THROUGHOUT IN ITS CHEMICAL
AND PHYSICAL STATE. • LINEAR INTERPOLATION:

• PHASE BOUNDARY => THE PRESSURE AND TEMPERATURE AT WHICH 2

PHASES COEXIST IN EQUILIBRIUM.

• TRIPLE POINT => THE POINT AT WHICH 3 PHASES ARE IN EQUILIBRIUM. • DEFINITION: THIS COMES FROM
THE EQUATION OF A STRAIGHT
• BOILING TEMPERATURE => THE TEMPERATURE AT WHICH THE VAPOUR LINE IN WHICH YOU CAN USE TO
PRESSURE OF THE LIQUID IS EQUAL TO THE EXTERNAL PRESSURE. FIND ANY VALUE OF P,T WITHIN A
DATA SET.
• VAPOUR PRESSURE => PRESSURE OF THE VAPOUR IN EQUILIBRIUM WITH
THE LIQUID/CONDENSED PHASE. • INTERPOLATION => ESTIMATING AN
UNKNOWN DATA POINT WITHIN AN
EXISTING SET OF DATA.
SINGLE COMPONENT PHASE DIAGRAMS
• A PHASE DIAGRAM OF A SINGLE COMPONENT. SINGLE COMPONENT PHASE DIAGRAMS

• USE OF THE CLAPEYRON EQUATION: • CLAUSIUS-CLAPEYRON EQUATION:

dP Δ S Δ H
= trs = trs
dT ΔtrsV TΔtrsV
• DEFINITION: THE SLOPE OF A PRESSURE VS TEMPERATURE • DEFINITION: TELLS YOU HOW THE VAPOUR PRESSURE CHANGES WITH TEMPERATURE.
PHASE BOUNDARY IS EQUAL TO THE ENTROPY CHANGE OF
THE TRANSITION, DIVIDED BY THE CHANGE IN VOLUME. • DIFFERENCES WITH THE CLAPEYRON EQUATION:
• USED TO CALCULATE THE ENTHALPY OF VAPORIZATION WHEREAS CLAPEYRON CAN BE
• STANDARD BOILING TEMPERATURE => THE TEMPERATURE AT USED FOR ANY PHASE TRANSITION. CLAUSIUS-CLAPEYRON MAINLY USED FOR
WHICH LIQUID AND VAPOUR EXIST IN EQUILIBRIUM AT 1 BAR. VAPORIZATION, BUT ALSO FOR SUBLIMATION.
• WITH CLAUSIUS, THE INTEGRATION ALLOWS YOU TO VISUALIZE THE COEXISTENCE CURVE
• ASSUMPTION OFTEN MADE: ΔH IS KEPT CONSTANT ACROSS FOR THE DIAGRAM, COMPARED TO A LINEAR DEPICTION. SO IT IS A BETTER
THE TEMPERATURE RANGE. APPROXIMATION THAN CLAPEYRON WITH CONSTANT SLOPE.
PRESSURE-COMPOSITION DIAGRAMS LEVER RULE

• IT SHOWS THE VARIATION OF VAPOUR PRESSURE WITH COMPOSITION. • A BINARY PHASE DIAGRAM SHOWS THE
RELATIVE AMOUNTS OF TWO PHASES
• ABOVE THE BLUE CURVE, EVERYTHING IS LIQUID (HIGH PRESSURE). BELOW (VAPOUR AND LIQUID) IN EQUILIBRIUM.
THE GREEN CURVE EVERYTHING IS VAPOUR (LOW PRESSURE) AND IN- • TO DETERMINE THESE AMOUNTS WE CAN
BETWEEN EXISTS BOTH VAPOUR AND LIQUID. USE THE LEVER RULE:
𝑛𝛼𝑙𝛼 = 𝑛𝛽𝑙𝛽
TEMPERATURE-COMPOSITION DIAGRAMS • α AND β REPRESENT THE TWO DIFFERENT
PHASES SUCH AS LIQUID AND VAPOUR.
• I T S H O W S T H E VA R I AT I O N O F
TEMPERATURE WITH COMPOSITION. • OTHER USEFUL RELATIONS TO KEEP IN
MIND ARE:
• AT HIGHER TEMPERATURES (ABOVE
𝑛 = 𝑛𝛼 + 𝑛𝛽
THE GREEN CURVE) EVERYTHING IS
VAPOUR, AND BELOW THE BLUE
zAn = xA,α nα + xA,β nβ
C U RV E E V E RY T H I N G I S L I Q U I D
BECAUSE IT IS COOLER. IN-BETWEEN • THE FIRST MEANS THE TOTAL NUMBER OF
EXISTS BOTH VAPOUR AND LIQUID. MOLES AT A PARTICULAR PRESSURE IS
USE COMMON SENSE WHEN LOOKING THE SUM OF THE MOLES OF SUBSTANCE
AT THESE DIAGRAMS TOO. IN THE LIQUID AND VAPOUR PHASES.
• THE SECOND MEANS THE TOTAL AMOUNT
• IN THE DIAGRAM DISPLAYED THE O F C O M P O N E N T A AT A S P E C I F I C
CURVES GO FROM TOP LEFT TO RIGHT COMPOSITION IS EQUAL TO THE SUM OF
BOTTOM, BUT THEY COULD ALSO GO THE AMOUNTS OF A IN THE LIQUID AND
FROM THE OTHER WAY AROUND. THIS VAPOUR PHASES.
DEPENDS ON WHETHER COMPONENT A • X IS OFTEN TAKEN TO BE THE LIQUID
IS MORE OR LESS VOLATILE THAN B. PHASE AND Y THE VAPOUR.

• IF A IS MORE VOLATILE THAN B, THEN • TO DETERMINE AMOUNTS FROM A PHASE

THE VAPOUR WILL ALWAYS BE RICHER DIAGRAM IT IS GOOD TO USE THE ABOVE
IN A THAN B, WHICH RESULTS IN THE THREE EQUATIONS TO FIND ALL YOUR
VAPOUR CURVE BEING TO THE RIGHT UNKNOWNS.
OF THE LIQUID CURVE.
• YOU CAN FIND L IN THE LEVER RULE BY
• IF A WAS LESS VOLATILE THAN B, USING A RULER TO MEASURE OR FROM
THEN YOU WOULD EXPECT THE TABULATED DATA.
CURVES TO BE FLIPPED FROM RIGHT
TO LEFT.
AZEOTROPES PARTIALLY MISCIBLE LIQUIDS
• A MIXTURE OF LIQUIDS IN WHICH THEIR COMPOSITION CANNOT BE • PORTRAYED ON A TEMPERATURE-COMPOSITION DIAGRAM.
CHANGED BY FURTHER HEATING. HENCE THE LIQUID AND VAPOUR ARE
BOTH EQUALLY CONCENTRATED IN THE SAME COMPONENT. • UPPER CRITICAL SOLUTION TEMPERATURE => THE TEMPERATURE ABOVE WHICH 2
LIQUIDS FULLY MIX. OCCURS BECAUSE THERMAL MOTION (kBT) OVERCOMES
• HIGH-BOILING AZEOTROPE (MAXIMUM) OCCURS WHEN THERE ARE INTERMOLECULAR FORCES .
FAVOURABLE INTERACTIONS BETWEEN A AND B WHICH REDUCES THE
VAPOUR PRESSURE BELOW THE IDEAL PRESSURE PREDICTED BY RAOULT’S • LOWER CRITICAL SOLUTION TEMPERATURE => THE TEMPERATURE BELOW WHICH 2
LAW. (LEFT SHOWN) LIQUIDS FULLY MIX. OCCURS BECAUSE INTERMOLECULAR INTERACTIONS AT
LOWER TEMPERATURES ENABLE MIXING BETWEEN COMPONENTS. THIS TYPE OF
• LOW-BOILING AZEOTROPE (MINIMUM) OCCURS WHEN THERE ARE INTERACTION BREAKS DOWN AT HIGHER TEMPERATURES.
UNFAVOURABLE INTERACTIONS BETWEEN A AND B WHICH LEADS TO AN
INCREASED VAPOUR PRESSURE COMPARED TO THE IDEAL. (RIGHT SHOWN).
RAOULT’S LAW

• STATES THAT THE PARTIAL PRESSURE

OF AN IDEAL SOLUTION IS
PROPORTIONAL TO THE MOLE FRACTION
OF THE COMPONENT AND THE VAPOUR
PRESSURE OF THE PURE LIQUID:
𝑝𝐴 = 𝑥𝐴 𝑝𝐴∗
• THE RULE IS OBEYED MORE CLOSELY AS
THE SOLUTION APPROACHES PURITY –
SO AS MOLE FRACTIONS APPROACH 1.

• W H Y D O E S VA P O U R P R E S S U R E S
D E C R E A S E AT L O W E R M O L E
FRACTIONS?
• AT LOWER MOLE FRACTIONS
THERE ARE GREATER IMPURITIES,
WHICH INCREASES ENTROPY.
• THE SYSTEM WILL HAVE LESS OF
A T E N D E N C Y TO B E I N T H E
VAPOUR PHASE (EVEN HIGHER
ENTROPY), SO IT WILL MOST
LIKELY BE IN THE LIQUID PHASE.