Phase Change diagrams Thermal chart

- Couple of things to note about this phase change diagram for water
- During a phase change (example where a solid is changing to a liquid and vice
versa etc) the temperature stays constant
- However, what changes during a phase change is the heat energy heat
energy is either added or released
- The different slopes show that u r in a phase Represents by Q = mcAT see
below
- The slopes are also different in these varying of phases
- During phase changes where heat energy is added are endothermic
melting and boiling (we are physically adding heat)
- During phase changes where heat energy is removed are exothermic
freezing and condensing (we are physically removing heat)

Equation of phase changes

Enthalpy of Fusion and Vaporisation or
latent heat
-

- The enthalpy of fusion = solidification measures the energy you need to convert:
o Solid to Liquid (melting)
o Liquid to solid (freezing)
- The enthalpy of vaporisation (gas to liquid) measures the energy you need to convert:
o Liquid to Gas (boiling) or vaporising
o Gas to Liquid or condensing
- The enthalpy of vapourisation
- The energy required to make the phase change is measured by the equation Q = mL
Q (kJ/mole) (that is m = mass (in moles) and L = Lf (latent heat of fusion) or Lh (latent heat
of vaporisation) (in Joules/mole)
- Looking at the slopes of the diagram there is an interesting point to be made:
o If you have a constant mass, the bigger the heat capacity (Q) then the smaller the
specific heat because of the slope equation on the picture that
Rise/run = delta T/Q
Q = mcdeltaT and thus
deltaT/Q = 1/mc
If m is constant
Bonds and Interactive forces
Among the interactive forces b/w molecule ion to ion interactions are the strongest -
have the highest lattice enthalpies and high MP and BP
London Dispersion forces: This is the weakest intermolecular force b/w atoms
these arise due to temporary dipoles formed b/w neighbouring molecules when the
electrons arrange themselves In a certain way forming a transient (short lasting)
force
o Dispersion forces increase with increasing number of electrons and increasing
surface area
o The only force b/w the noble gases are London dispersion forces Thus the only
way we can turn our noble gases to liquid (liquefaction) through dispersion forces
o CO2 even tho it has polar bonds is a non polar molecule and only has dispersion
forces explains the passage of CO2 vapour to dry ice (gas to solid)

Hydrogen bonding:
Hydrogen bonding is peculiar in that it occurs only when a H bond is attached to one of the
three electronegative atoms (NOF) forms a bond or link with another NOF in another
molecule

Water has the highest boiling point due to the presence of the OH bond means
But Why does SnH4 have a higher boiling point than CH4 This is due to the
presence of dispersion forces The higher molecular weight (x axis) of Sn means
that it has more dispersion forces than C and thus a higher boiling point
Bonds in organic chemistry

Vapour Pressure
o Unique property of liquids
o If u take water in a container and allow it to start evaporating the space above the
surface of the water will start getting water molecules and that means its a gas now
gases have pressure So as that builds up, these particles floating above the
water can go back into the water unless they are taken away If you put a lid on
the water, the particles are trapped the particles go back into the water
o Then you have a rate where the exiting evaporation rate = entering condensation
rate and you reach equilibrium
o Once you reach equilibrium reach a constant pressure this is called the vapour
pressure of that liquid and this is an example of dynamic equilibrium that is there
is no net change when the particles leave the water they also enter the water
o Thus the normal boiling point of a liquid where it equals its vaporising point is 1 atm
(that constant pressure)
Maxwellian Boltzmann energy
distribution
Temperature is proportional to Average kinetic energy

- In any system, the particles present will have a very wide range of energies. For gases we
can show this on the Maxwell Boltzmann distribution
- The area under the curve is a measure of the total number of particles present

speed or energy

In the case of liquids, that also follow a Maxwellian distribution, the higher energy
molecules boil first BUT All molecules require extra energy to change phase and this is the
activation energy or the enthalpy of vaporisation
Both graphs here have the same number of particles and thus the same amount of area
under the graphs the one of the left is higher because it is more narrow.

Towards the end the high energy gaseous molecules reach the activation energy
required and reach the temperature of vaporisation or the boiling point
Vapour pressure is an equiibirium b/w the liquid and gaseous phase of a substance,
but, when you add heat to the liquid more particles enter the gaseous phase
enough particles at the gaseous phase Those gaseous phase molecules are at a
pressure that is equal to the surrounding atmosphere and that is the vapourisation
or the boiling point
The boiling point is where the vapour pressure = atmospheric pressure when this
happens there are enough particles that can become gas
Basically now the pressure of the layer, the particles can now enter the atmosphere
those particles that enter the atmosphere has the effect of removing the gaseous
molecules from the equilibrium b/w the liquid and gas
Remember Le chats principle, once you lose the equilibrium, the system will try to
oppose the change your removing the product (gas) and the system tries to make
more of the product alas make more gaseous molecules and thus you have boiling
Phase diagram

A substance exists as a solid, a liquid or a gas depending on its temperature and

pressure.
Triple point = the point at which a solid, liquid and gas coexist
Critical point is the point at the highest temperature and pressure
the critical temperature is the temperature at which above it the substance cannot
be a liquid higher than the critical temperature then no increase in pressure can
turn the vapour into a liquid lower than the critical temperature there are
pressures at which the vapour can liquefy
Water is one of the few substances for which the solid is less dense than the liquid.
Revise Point 24 of this dnt understand
Supercritical fluid exhibits behaviour of both gas and liquid phases
Always look at what happens when you keep temperature constant but increase
pressure etc
If ur at a constant pressure and you increase temperature It will favour the higher
energy matter going from solid liquid - gas at these points
There are sometimes you go from solid to gas which is called sublimation and
deposition (opposite) which happen only at very low temperatures and pressures
both below the triple point
this applies to water and perhaps not other phases an increase in pressure tends
to favour moving towards the liquid phase
Solution Chemistry

Effect of temperature/pressure on solubility of

gases
Henrys Law:

Note kH = henrys constant is

interchangeable with the equilibirium
constant

The solubility of a gas (concentration) is proportional to the partial pressure of that

gas above the liquid (vapour pressure)
Equation:
Concentration of liquid = solubulity x kH (Henrys constant) = Partial Pressure of
that liquid above the surface

The solubility represents the maximum amount of solute that can be dissolved in
solvent at a constant temperature
So if we decrease volume, we increase pressure, we are thus increasing solubility
However temperature and solubility are inversely proportional
Increase in temperature decreases solubility increasing the temperature,
increases kinetic energy, molecules move faster, intermolecular bonds and broken
and this allows more molecules to escape from the solution (making it less soluble)-
The inverse of the Henry Law is molar solubility which is the number of moles of
solute dissolved into 1L of solution point 34 not really sure
Colligative properties

Colligative properties depend on the number rather than the type of dissolved
particles
The boiling point of elevation and the freezing point of depression serve to keep the
solution in the liquid phase for longer - make it harder to boil and so it will
increase its time in liquid phase and make it hard to freeze, also keeping it as a liquid
for longer
Need to know i = vant hoff factor it corrects for the number of solute particles vs
the number of dissolved particles that produces e.g: If you have Calcium Chloride
(CaCl2 you will yield 3 molecules 1 Ca and 2 Cl = 3 molecules 3 = vant hoff
factor Remember colligative properties cares about the number!!!
Vapour pressure Raoults Law:
Explains how adding a solute to a solvent can change the vapour pressure over a
solution
There are 2 forms of it both have different formulas :
o A Non volatile solute dont contribute their own vapour pressure because
the solute does not evaporate lowers overall vapour pressure because
there is less solvent that is evaporating into the gaseous phase
o Volatile solute both components contribute a vapour pressure and
evaporate this is the case when you mix 2 mixable things together We
could have a liquid solute and a liquid solvent OR gas solute and liquid
solvent
Non
volatile solute:
Lets say we
have a solution
that is 90%
solvent and 10%
non volatile
solute that
would have the
effect of
reducing the
vapour pressure
of that solution
by 10% by what
it would be if it
was pure
solvent Your
reducing vapour
pressure
because you are
adding
components that dont contribute any vapour pressure and thus you are seeing a
lower vapour pressure than you would with a pure solvent
Volatile solute: You have a vapour pressure b/w Component A and Component B
lowers overall vapour pressure
Raoults law is particularly good for two overall solutes that are mixed together with
each other
However, every once in a while you will get a question that considers how the
process of dissolving influences Raoults Law and you will see a deviation in the
positive and negative direction diff to Raoults Law
Raoults law has a limitation it only holds for mole fractions 1 or less (i.e really
dilue solutions)
Boiling Point Elevation and Freezing point of Depression
*Note: remember when calculating these if you are asked for the new boiling point, dont
forget to add the change in boiling/freezing point to the old boiling/freezing point
Boiling point of elevation:
Boiling occurs when vapour pressure = atmospheric pressure as we said before
When you have dissolved substances in water if its a non volatile particle
(doesnt evaporate) then you have more solute at the surface
Remember what creates the vapour pressure is that thin layer of particles on top of
the liquid gas interaction
As you add more interfering solute particles there is less surface area for these water
molecules to enter the
gaseous phase so at a
given temperature there is
fewer particles that will
exist in the gaseous phase
because some of the
surface area has been
taken up by these solutes
This means at any given
temperature fewer
molecules in the gaseous
phase (vapour pressure) >
vapour pressure is lower
and in order to get a
vapour pressure that
competes with
atmospheric pressure you have to raise the temperature This is why the boiling
point elevates when solutes are added to solvents

Freezing point of depression

You have to lower the temperature even further in order to freeze the material
Remember when your taking a liquid and freezing it into a solid, a lattice structure
develops and that means the solvent particles are interacting with each other in such
a way that it is forming a fairly rigid structure
What happens when you add more particles (solute) they get in the way and
interfere with the solvent particles forming the lattice becomes harder to freeze
the object need to lower the temperature further i.e: take more heat energy out
of the environment in order for the lattice to form freezing point depresses
Osmotic pressure
Last colligative property
Created by waters desire to equalise concentrations of solute on both sides of semi
permeable membrane
Usually when you see osmotic pressure its been equalised by hydrostatic pressure
remember P = density x g x y and so the hydrostatic pressure is all about the depth
of the water and how much pressure there is at each depth but what is neutralising
hydrostatic pressure is osmotic pressure due to concentration gradients created by
the hydrostatic pressure
Osmotic pressure serves to balance out hydrostatic pressure
Reaction rates and Equilibrium
Rate Law:
The rate law is a mathematical expression