CHEM1201 NOTES

Topic 1: Colligative Properties

Solid --> liquid and liquid --> gas both require an input of energy

Intermolecular attractions are much weaker than covalent bonds

 often called non-covalent attractions

London/Dispersion Interactions
the attraction between species which results from electrostatic attraction of opposite charges
- arise because at a particular instant, electrons are unevenly distributed, forming an
instantaneous dipole

- species must be relatively close to each other

- size dependent:

 small size => lower

 large size => higher

- When an instantaneous dipole forms, we say the species has been polarised
- Polarisation of one species can induce a dipole in an adjacent species due to
electrostatic repulsion => known as: dipole-induced dipole attraction

Ne δ Ne Ne Ne
+¿¿
+¿¿ −¿¿ +¿¿ −¿ δ ¿ −¿¿
e.g. δ ---------> δ δ δ
−¿¿
Electrons repel from initial δ charge, and move to the
opposite end, forming a new dipole

ZEFF: ‘effective nuclear charge’ : the positive nuclear charge that is experienced by an electron

Polarisability
the ease at which charge distribution can be distorted
 the greater the polarisability, the more easily the electron cloud can be distorted to give
an instantaneous dipole

Trend:

Polarisability increases down a group

  valence electrons are further away from the nucleus, so their force of attraction to the
nucleus is weaker, thereby allowing them to be moved more easily
 ZEFF decreases
Polarisability decrease across a period
 number of protons increase -> greater (+) charge
-> greater force of electrostatic attraction to the nucleus experienced by each electron
-> electrons are harder to move
 ZEFF increases

 Polarisability influences boiling/melting point

Shape

The shape of a molecule influences dispersion forces, because the greater the surface area, the
greater the region of contact between molecules

e.g. Pentane (C 5 H 12) Neopentane (C 5 H 12)

linear molecule spherical molecule

➞ larger surface area ➞ smaller surface area
➞ enhanced intermolecular contact ➞ diminished intermolecular
➞ increased dispersion forces contact
➞ decreased dispersion forces

Size

Large molecules have electrons further away from nuclei, which causes electrons to have a
reduced electrostatic attraction to nuclei, in turn making them easier to distort to form
instantaneous dipoles and thereby dispersion interactions
e.g.
Molecular
<------size Name
decreases------ Structure Boiling -----dispersion attraction------
Formula Point decreases
C3H7OH Butan-1-ol 118° C

C3H7OH Butan-2-ol 99° C

C3H7OH 2-methylpropan- 82° C

2-ol

Electrons in higher orbitals are ‘shielded’ by electrons in lower orbitals to have lower ZEFF

E.g. 1 Which substance has the strongest dispersion forces?

a) H2O b) H2S c) H2Se d) H2Te

Solution:

the only difference between the four molecules is the non-hydrogen atom

All four atoms are in the same group.

Te is lowest down, so has the greatest dispersion forces

∴ answer is d)

E.g. 2 Which one of the following atoms has the smallest polarisability?
a) Ar b) He c) Kr d) Ne

Solution:

all atoms in the same group

He highest up, so has smallest polarisability

∴ answer is b)
E.g. 3 Which one of the following pairs has compounds arranged with species with the highest
polarisability first?
a) CBr4 and CI4
b) H2O and H2Se
c) NH3 and NF3
d) C6H14 and C4H10

Solution:

a) Br is higher than I so no
b) O is higher than Se so no
c) F is a large atom so yes
d) C6H14 has less surface area so no

∴ answer is c)

Dipole-dipole interactions
attraction between species which have permanent dipoles
- strongest in solids, but also present in liquid and gas
- dispersion interactions will also be present

e.g.
−¿¿
δ H−Clδ
+¿¿

δ H−Clδ
+¿¿ −¿¿

dipole-dipole attraction

Hydrogen bonding
- An extreme form of dipole-dipole interaction
- Occurs when a H atom, covalently bonded to O, F or N, is attracted to the lone pair on
an adjacent electronegative atom (also O, F or N)
- Influences boiling point of water
- Is an interaction between a H-bond donor and a H-bond acceptor

In general:
H-bond
−¿¿
δ δ +¿¿
−X −H : X−¿
X =F , O , N
H-bond donor H-bond acceptor
- supplied H - supplies lone pair
 atom

Ion-Dipole Attractions
Electrostatic attraction between a charged ion and a molecule that has a dipole
- responsible for dissolution of ions in water

the ions are hydrated

- strongest for small ions with large charges (large charge density)
e.g. Al3+

- Ion-dipole attractions allow salts to be used as drying agents, as water is removed via
ion-dipole attraction to the ions of tha salt
e.g. Na2SO4

Protic solvent
A substance that is a hydrogen bond donor and a hydrogen bond acceptor
- requires a hydrogen covalently bonded to oxygen, fluorine or nitrogen

e.g. ethanol
δ −¿¿
.. δ +¿¿
acceptor CH 3−O−H donor
..
- attracts + ions - attracts – ions

- protic solvents can dissolve both + and – ions

 Aprotic solvent
A substance that is only a hydrogen bond acceptor
- requires a lone pair on an electronegative atom
- has no O-H, N-H or F-H bons
e.g. dimethyl ether

..δ −¿¿ δ +¿¿

CH 3−O−CH 3
..

acceptor
- attracts + ions

- aprotic solvents only dissolve cations

Summary of Intermolecular Forces

Interacting Particles
−¿¿
2e (atoms, molecules, ions)
e−¿¿
ions present ions not present

ions only ions and molecules Polar and non-polar Non-polar

molecules molecules

Ionic bonding Ion-dipole interactions Dipole-induced dipole Dipole-induced

interactions dipole interaction
or
Dispersion
Polar molecules forces

H bonded to
N, O or F

Dipole-dipole Hydrogen
interactions bonding
Limonene Lecture Demonstration:

Adding water to an ethanol + limonene (orange oil) solution => causes it to become
cloudy

Reason why:

limonene ethanol water

C 2 H 5−OH

non-polar polar
polar

non-polar

The non-polar region of the ethanol allows the limonene to dissolve

Adding water causes ethanol to dissolve with the water, reducing its non-polar influence
 this causes the limonene to no longer be dissolvable in the now polar solvent, in turn
causing a cloudy suspension to form

E.g. Which member of each pair has the strongest intermolecular attraction?
1: a) HOCH2CH2OH b) CH3CH2CH2OH
2: a) CH3COOH b) (CH3)2C=O
3: a) HF b) HCl

Solution:
1: a) because there are 2 sites for H bonding
2: a) because it is a H-bond acceptor and donor, while b) is only an acceptor
3: a) because it can form hydrogen bonds due to the presence of a F atom

E.g. 2
X-H ⋯ Y represents hydrogen bonding between X and Y. Name two properties of X and Y which
are necessary for hydrogen bonding to occur

Solution:
X and Y should be one of the electronegative elements: F, O or N

Y should have a lone pair of electrons

E.g. 3
What is the descending order of boiling points of compounds:
I CH3-CH2-CH2-CH3
II CH3-O-CH2-CH3
III (CH3)3CH
IV CH3-CH2-CH2-OH

a) III > I > II > IV

b) IV > II > III > I
c) II > IV > III > I
d) IV > II > I > III

Solution:
IV is the highest because it is the only compound which can form hydrogen bonds

II is the next highest because it contains an electronegative element (oxygen) so therefore

forms dipole-dipole attraction

I is straight chained while III is branched, so I has more surface area to form dispersion
attraction

∴ answer is d) IV > II > I > III

E.g. 4
Which of the following pairs of ions is arranged so that the ion with the largest charge density is
listed first
A) K+ and Rb+
B) Rb+ and K+
C) Br- and Cl-
D) Cl- and F-

Charge density is ‘charge to volume ratio’

Each pair has equal charge. Hence we require the first ion of the correct pair to be smaller

Hence answer is A

For a solute to dissolve in a solvent, 3 events must occur:

1. Solute particles separate

Solute (aggregated) + heat -> solute (separated)

Is an endothermic process
 -> requires energy input

2. Solvent particles separate

Solvent (aggregated) + heat -> solvent (separated)

Also endothermic

3. Solute and solvent particle mix

Solute (separated) + Solvent (separated) -> solution

Is exothermic

The total Δ H when a solution forms is Δ Hsoln

Δ H soln= Δ H solute + Δ H solvent + Δ H mix

If the sum of the endothermic terms is smaller than the exothermic term:

i.e. Δ H solute + Δ H solvent < Δ H mix

Δ H soln <0 => ∴ process is exothermic

-> mixing will occur to an appreciable extent

If the sum of the endothermic terms is larger than the exothermic term,

i.e. Δ H solute + Δ H solvent > Δ H mix

Δ H soln >0 => ∴ process is endothermic

-> mixing will not occur to an appreciable extent

Lattice Energy
the lattice energy of an ionic solid is a measure of the strength of the electrostatic interactions
between oppositely charged ions
- it works to keep ions in the solid state

E.g. Δ H lattice ( KF )=−821 KJ / mol

so for the dissolution of KF in water:

 −¿: ΔH lattice ( KF )=821KJ/ mol¿
+¿+F( g) ¿
KF s → K g

H2O molecules are separated and hydrate K+ and F- ions

+ ¿+ F−¿¿ ¿
(aq )

+¿+ F −¿→
: Δ H hydration=−819 KJ /mol
K ¿
aq
¿
K (g) (g)

∴ Δ H solution =−Δ H lattice + Δ H hydration

¿ 821−810
¿ 2 KJ /mol

Δ H hydration depends on charge density (charge to volume ratio)

The higher the charge density:

 the more + the ΔH ❑hydration

 thermodynamically more favourable

Solutions & Entropy:

The solution process involves a ‘competition’ between Δ H soln and Δ S soln

Systems tend towards a state of lower enthalpy and higher entropy

The magnitudes of Δ H soln and Δ S soln determines whether a solution will form (Gibbs free
energy)

Vapour Pressure
- liquid molecules move at various speeds
- at any instance some liquid molecules process enough kinetic energy to overcome IMFs
and escape into the gas (vapour) phase
- the weaker the IMFs, the larger the number of molecules that can escape -> the higher
the vapour pressure

At a fixed temperature, the vapour pressure of a liquid is a measure of the tendency of its
molecules to escape from liquid and enter the gas phase

As temperature increases, vapour pressure increases

A substance with a high vapour pressure is said to be volatile

Vapour pressure must be stated for a fixed temperature

E.g. 1
a) Which ion, Cl- or Br- is more strongly attracted to water?

higher the charge density => stronger the ion-dipole interaction

both ions have same charge

∴ smaller ion has greater charge density

∴Cl- is more strongly attracted to water

b) Which ionic compound, CaCl2 or CaI2 would you expect to have more negative Δ H hydration
stronger ion-dipole interaction => more – the Δ H hydration

Cl- has greater charge density than I-

∴ CaCl2 will have a more negative Δ H hydration

E.g. 2 Which terms are matched correctly?

A. high vapour pressure high Δ H vapourisation value

B. high Δ H vapourisation value low boiling points
C. low vapour pressure high boiling point
D. low boiling point low vapourisation rates

Δ H vapourisation refers to the amount of energy required to convert one mole of liquid to one mol
of vapour
∴ high Δ H vapourisation implies less vapourisation, so hence low vapour pressure
=> ∴ A is incorrect

high Δ H vapourisation implies higher boiling point

=> ∴B is incorrect

high boiling points means less vapourisation would occur, hence vapour pressure would be low
=> ∴C is correct

low boiling point would mean vapourisation would occur more easily and hence more
frequently
=> ∴ D is incorrect
Drinking Bird

Water evaporates from the bird’s head

 this cools the head

Decrease in temperature condenses CH2Cl2 vapour

 Vapour pressure of CH2Cl2 decreases around the head relative to the abdomen

As a result of the greater CH2Cl2 vapour pressure in the abdomen, liquid CH2Cl2 is formed up the
neck and into the head

 process repeats itself

Concentration
the proportion of a substance in a mixture
- variety of ways of expressing concentration:
Molarity (M) and molality (m)

n(solute )
M= molarity
litres of solution

n(solute)
m= molality
kg of solvent

Molality is useful when molarity keeps changing.

Molarity changes as temperature changes

Molality does not change as temperature changes

(volume is dependent on temperature while mass is not)

Molarity ≈ molality, in very dilute solutions

because Dsolution ≈ Dsolvent
(density)

volume of solute
Volume % (%v/v/) ¿ ×100
volume of solution
 mass of solute
Weight % (%w/w/) ¿ ×100
mass of solution

Mole fraction
n(A)
χ ( A )=
n ( A ) +n (B)

where A is the solute and B is the solvent

χ ( A ) + χ ( B )=1

E.g.
The freezing point of water is lowered by adding rock salt (NaCl). One manufacturer suggests
you agg 1130g of NaCl (molar mass = 58.5 g/mol) to 7250 g of ice (molar mass = 18 g/mol) and
put it in a large freezer. Calculate:
a) χ ( NaCl )
b) molality of the solution

Solution:
n ( NaCl )
a) χ ( NaCl )=
n ( NaCl ) n ( H 2 O )

1130
58.5
¿
1130 7250
+
58.5 18

≈ 0.0458(3 sig . fig .)

n ( NaCl )
b) molality ¿
kg ( H 2 O )

1130
58.5
¿
7.250

−1
≈ 2.66 mol kg (3 sig. fig.)

Colligative
means ‘depending on the collection’
Colligative properties depend on the collective effect of the number of solute particles (not the
type)
Includes:
- boiling/melting/freezing point
- vapour pressure
- osmotic pressure

Non-volatile
having no measurable vapour pressure

- adding a non-volatile solute to a solvent always lowers the vapour pressure ( Δ p ) of the
solvent
- the extent of Δ p is proportional to the solute concentration

 Δ p ∝ number of particles
( Δ p is a colligative property)

Vapour Pressure Depression

Consider a closed system of a pure solvent, at a fixed temperature, with rate of condensation =
rate of vaporisation
 solvent (l ) ⇌ solvent (g )

Adding a non-volatile solute:

The presence of a non-volatile solute (e.g. glucose, urea, ethylene glycol) alrters the behavour
of the solvent

The non-volatile solute disrupts the evaporation process by attracting solvent particles via IMFs

The presence of a non-volatile solute does not affect condensation, as the non-volatile solute is
not present in the surrounding vapour

E.g. 1: How many of the following unit conversions require knowledge of density?
i) % w/v to mole fraction
ii) %w/v to molarity
iii) mole fraction to molality
iv) molality to molarity

A1
B2
C3
D4

n(A)
i) g/100mL → moles is mass bases. Going from volume to mass
n ( A ) + n(B)
∴ YES
−1
ii) g/100mL → mol L volume to volume so NO

n ( A)
iii) → mol kg−1 mas to mas so NO
n ( A ) +n(B)

−1 −1
iv) mol kg →mol L mass to volume so YES

∴ ANSWER IS B

E.g. 2 Glucose, C6H12O6 (18.016g, 0.1mol) a non-volatile, non-electrolyte, was dissolved in water
and the volume made up to 1L with water. The resulting solution, at 25° C, had a density of
1.0058 mL-1

Calculate:
i) the %w/v
ii) the molarity

i) 18.016g in 1L
∴ 1.802g in 100mL

∴ %w/v = 1.802 % w/v

0.1
ii) molarity ¿
1
−1
¿ 0.1 mol L

A solution containing a non-volatile solute and a solvent (e.g. H2O) forms spontaneously
because of the increase in entropy that accompanies mixing.
In effect, the solvent molecules are ‘stabilised’ in the liquid state by this process, and thus have
lower tendency to escape into the vapour phase
(they don’t need to vapourise to increase entropy, because their entropy has already been
increased)

Therefore when a non-volatile solute is present, the vapour pressure of the solution is lower
than the vapour pressure of the pure solvent, at a fixed temperature.

A pure solvent vapourises because the vapour has greater entropy than the liquid

A solvent in solution has greater entropy than the pure solvent, so hence a lower tendency to
vaporise in order to gain entropy

Raoult’s Law
predicts that the vapour pressure of a solvent in a solution is proportional to the amount of the
solvent present

Δ p= χ solute ∙ P° solvent

where Δ p is the rate at which vapour pressure lowers

χ solute is the mole fraction of the solute

P ° solvent is the vapour pressure of the pure solvent at a fixed temperature

- In an ideal solution, particles experience the same IMFs in solution as they do in pure
liquid
i.e. solvent-solvent IMFs = solute-solute IMFs = solute-solvent IMFs

 same energy required for solvent molecules to break away from the surface in either
case
-> very unlikely

Psoln. = P° solvent −Δ p
Pure liquid A Pure liquid B Mixture of A + B
χ A =0.5 , χ B =0.5

(DIAGRAMS)

More ways the

molecules can be
arranged
∴ greater entropy
∴ Δmix S> 0

Non-Ideal Solutions

Some B molecules B molecules escape B molecules escape

escape to vapour, to more easily less easily
exert a vapour pressure ↓ ↓
vapour pressure of vapour pressure of
B > predicted by B > predicted by
Raoult’s law Raoult’s law

A-B interactions A-B interactions A-B interactions

= A-A interactions < A-A and > A-A and
= B-B interactions B-B interactions B-B interactions
↓ ↓↓
Ideal solution: Positive deviation Negative deviation
PB = χ B P B ° PB > χ B PB ° PB < χ B PB °

e.g. benzene & toluene e.g. CH3CH2OH & C6H4 e.g. CH3(C=O)CH3
(propanone) & H2O
CH3
Raoult’s law works best for dilute solutions, as they are more likely to have A-B = A-A = B-B

E.g. 1 Consider 2 solutions, one formed by adding a mass of glucose (C 6H12O6) to 1L of water,
and the other by adding the same mase of sucrose (C12H22O6) to 12L of water.

Are the vapour pressure of the 2 solutions the same? Why or why not?

M(sucrose) > M(glucose)

∴ n ( glucose )> n( sucrose)

∴ χ ( glucose ) > χ (sucrose )

∴ Δ p ( glucose solution ) > Δp( sucrose solution)

↑ ∵ Δ p ∝ χ solute
vapour pressure
depression

∴ P glucose soln. < P sucrose soln.

E.g. 2 Calculate the vapour pressure of water above a solutionprepared by adding 22.5 g of
lactose (C12H22O11) (molar mass = 342.296 g mol-1) to 200g of water
(molar mass = 18.016 g mol-1) at 339 K. Vapour pressure of pure water at 338K is 187.5 torr

Δ P= χ solute × P ° H O
2

n ( lactose )
¿ ×187.5
n (lactose ) +n( H 2 O)

22.5
342.298
¿ × 187.5
22.5 200
+
342.298 18.016

¿ 0.005886 ×187.5

¿ 1.10 torr

Psoln. =P ° H O −Δ P
2

¿ 187.5−1.10
 ¿ 186.4 torr

E.g. 3 Consider a solution of 2 liquids in which the molecules interact less favourable than they
do in the individual liquids. Which one of the following statements is correct about the
solution?
A. It will be an ideal solution
B. It will deviate negatively from Raoult’s law
C. It will deviate positively from Raoult’s law
D. It will follow Raoult’s law

A-B interactions < A-A and B-B interactions

∴ positive deviation

∴ ANSWER IS C

Boiling Point Elevation

Boiling point
the temperature at which vapour pressure = (external) atmospheric pressure

The vapour pressure of a solution is lower than the vapour pressure of the pure solvent (at all
temperatures)
 ∴ the vapour pressure of a solution is lower than the external pressure at the solvent’s
boiling point

 ∴ a higher temperature is needed to raise the solution’s vapour pressure to equal the
external pressure

 ∴ solutions have greater boiling points than their pure solvents

Pure H2O at 100° C

H2O(l) ⇌ H2O(g)

---- more entropy -->

Add some sugar to the H2O

H2O(l) molecules become more disordered relative to pure H2O(l)

H2O(g) molecules are not affected by the sugar, as sugar does not evaporate at 100° C
∴ less tendency for H2O(l)→H2O(g), because there is more entropy in H2O(l) + sugar than H2O(l)
Therefore, addition of a non-volatile solute to a solvent:
 reduced the vapour pressure of the solvent
 elevates the boiling point of the solvent

Freezing Point Depression

e.g. H2O at 0° C, 1 atm. pressure

H2O(l) ⇌HO 2 (s)

+ Non-volatile solute
 will interact with the H2O(l), reducing its ability to form H2O(s)
- cannot interact with H2O(s)
∴ will only affect H2O(l) →H2O(s)
NOT H2O(s)→ H2O(l)

To maintain equilibrium, H2O(s)→H2O(l) must be slowed down

 to do this, the temperature must be reduced

(Freezing point is where P H O =P H

2 ( s) 2 O(l) i.e. equilibrium)

∴ addition of a non-volatile solute reduces the freezing point of the solvent

Summary
Both freezing point depression ( Δ T f ) and boiling point elevation ( Δ T b) are proportional to the
concentration of the solute particles

 Δ T b and Δ T f are colligative properties

 Δ T b and Δ T f ∝ molality

 Δ T b=K b ( molality ), Δ T f =K f ( molality )

Kb = the molal boiling point elevation constant (° C kg mol-1)

Kf = the molal freezing point depression constant (° C kg mol-1)

Properties of the solvent

Each solvent has unique Kb and Kf values

E.g. If Kb = 0.5 ° C kg mol-1, then for every 1 mol of solute dissolved in 1kg of solvent, boiling
point will increase by 0.5° C

Molality is used instead of molarity, because molality is temperature independent

Boiling point is not a colligative property, the elevation of boiling point is colligative

E.g. 1 What is the freezing point of radiotor coolant that contains 2kg of ethylene glycol (molar
mass = 62.07 g/mol) and 5kg of water (molar mass = 18.016 g/mol)

Kf for water is 1.86° C kg mol-1

Tf for water is 0° C

Δ T f =K f × molality

n ( E .G .)
molality ¿
kg( H 2 O)

2000
62.07
¿
5

¿ 6.444 (4 sig. fig.)

Δ T f =1.86 ×6.444
¿ 11.99 °C

E.g. 2 Molal freezing point depression constant, K, is a property of which one of the following?
A a non-volatile solute
B solution
C a solvent
D a vapour

ANSWER C

Osmosis
- passive transport
- movement of water from low to high solute concentration over a semipermeable
membrane

- determines where H2O goes

- H2O is never actively transported

 ↓
- In order to control H2O movement, organisms must control osmosis

If a semipermeable membrane is placed between two solutions of different concentration,

solvent molecules move both ways through the membrane.
But the rate at which the solvent travels from less concentrated to more concentrated is faster
than the rate in the opposite direction

Hence there is a net movement from less concentrated to more concentrated

 this process is called osmosis

Osmotic pressure
the pressure required to prevent osmosis
given symbol π

e.g. desalinating a salt solution

 decreases entropy, and goes against osmosis

requires reverse osmosis:

pushing water, at high pressure, through a semipermeable membrane
(very energy intensive)
Osmotic pressure
The osmotic pressure is proportional to the number of solute particles in a given volume of
solution (molarity)

π ∝ molarity

π=molarity × R ×T

where R is the gas constant: R = 0.08206 L atm mol-1 K-1 and T is the temperature in Kelvin

If two solutions of identical osmotic pressure are separated by a semipermeable membrane:

- no osmosis will occur
- the solutions are said to be isotonic

Cells bathed in a hypertonic solution ( π solution > π ❑cells) will shrivel as a result of water moving out
of the cells
→known as crenation

Cells bathed in a hypotonic solution ( π solution < π cells ¿ will rupture because of water moving into
the cells
→ known as lysis

van’t Hoff factor (i)

relates the number of moles of solute to the number of particles in solution

e.g. iexpected(NaCl) = 2 (Na+ and Cl-)

iexpected(CaCl2) = 3 (Ca2+ and 2Cl-)

iexpected assumes: complete dissociation of solute, no ion ‘clumping’, ions moving independently
of each other
This assumption is not true, because ions clump together
E.g. NaCl in water:
Some Na+ and Cl- ions bump into each other, join and are counted as an ion pair => i.e
ONE unit

In very dilute solutions iexpected ≈ iactual

(less ion pairing)

The higher the charge density, the greater the ion pairing
 iactual deviates more significant;y from iexpected

The more concentrated the solution, the more ion pairing

Colligative Properties of Electrolyte Solutions

Δ T b=K b × molality ×i

Δ T f =K f × molality ×i

π=molarity × R ×T ×i

Δ p= χ solute × P ° solvent

n ( solute ) ×i
where χ solute=
n ( solute ) × i+ n( solvent )

True molality / True molarity

measured by weighing out solvent and solute

Osmolality / Osmolarity
measured by a colligative property: takes into account the number of particles in solution

osmolality ¿ i× molality

osmolarity ¿ i× molarity

osmolarity
i actual =
true molarity
*
osmolality
i actual =
true molality
* not on data sheet
E.g. A 2% (w/w) water-solution of H2SO4 (molar mass = 98.1 g/mol) freezes at -0.796° C

Kf for water is 1.86° C kg mol-1

The freezing point of pure water is 0.00° C

a) Calculate the molality of the solution

b) Calculate the van’t Hoff factor for this solution
c) Which of the following best represent sulfuric acid in a dilute solution:
H2SO4, H+ + HSO4- or 2H+ + SO42-

Solution:

a) 2% w/w means 2g(H2SO4) in 100g (solution)

∴ 2 g ( H 2 SO4 ) ∈98 g ( H 2 O )

∴ molality= ( 98.12 )÷ 1000

98

−1
≈ 0.208 mol kg (3 sig. fig.)

b) Δ T f =0−−0.796
¿ 0.796 ° C

Δ T f =k f ×molality ×i actual

ΔT f
∴ i actual=
K f × molality

0.796
¿
1.86× 0.208

≈ 2.06 ( 3 sig . fig . )

c) i ≈2 so tere are approximately 2 particles produced for every H2SO4 molecule

∴ dilute H2SO4 solution is best represented as: H+ + HSO4-

Topic 2: Kinetics
In chemistry, kinetics refers to how rapidly chemical reactions occur and mechanism refers to
how a chemical reaction occurs

Collision Theory
States that for a reaction to proceed, reactant particles must collide
- The more collision, the faster the reaction
- Used to explain why chemical reactions occur at different rates

- For a reaction to proceed, reactant particles must:

a) collide with sufficient energy to break reactant bonds

-> i.e. overcome the activation energy (EA)

b) be in an orientation favourable for breaking these bonds

Factors that affect reaction rate

Concentration
rate of reaction generally increases as reactant concentration increases
-> more reactant particles -> more collisions per unit of time -> more often a reaction

Temperature
rate of reaction generally increases as temperature increases
-> greater temperature -> greater kinetic energy -> particles move faster -> collide more
frequently

Phase and Surface Area

Uniformly dispersed -> collisions depend on concentration and temperature, and happen
(homogenous) everywhere

Heterogenous arrangement -> collisions, and hence reaction, only occurs at the interface
of reactants (where the two meet)
Greater the surface area, the greater the reaction rate

Solvent
nature of solvent can affect reaction rate

e.g. reaction of SN2 between CH3F and CH3CO2- occurs faster in a dimethylformamide (aprotic)
solvent rather than a methanol (protic) solvent

dimethylformamide: methanol:

−OH

aprotic protic
not a H-bond donor is a H-bond donor
i.e. no F-H, O-H or
N-H bonds

SN2 prefers aprotic solvents to react, as the formation of hydrogen bonds with protic solvents
hinders it from reacting

Catalyst effect
catalysts accelerate the rate of specific reactions

Reaction Rate
expressed as:
- concentration of reactant consumed
OR - concentration of product produced per unit of time

Units: mole per litre per unit of time

mol L-1 s-1

Consider a reaction A → B

Δ [ B ] −Δ [ A ]
Rate ¿ =
Δt Δt

Convention: reaction rates expressed as positive numbers

For a reaction aA →bB

Δ [ B ] −b Δ [ A ]
Rate ¿ =
Δt a Δt

E.g. 2SO2(g) + O2(g) → 2SO3(g)

Write the expressions for the reaction rate in terms of the rate of change of
concentration of each species

−Δ [ SO 2 ] −2 Δ [ O2 ] Δ [ SO 3 ]
= =
Δt Δt Δt

−Δ [ O2 ] −1 [ SO 2 ] 1 Δ [ SO 3 ]
= =
Δt 2 Δt 2 Δt

Rate law (rate equation)

describes the relationship between reaction rates and reactant concentration
- derived from experiment data

not on data sheet

For the reaction: aA + bB → cC + dD

rate law has form:

x y
Rate ¿ k [ A ] [ B ]

where k is the rate constant

-> depends on type of reaction, and reaction conditions

and x and y are the experimentally determined reaction orders

(x is the reaction order with respect to A, y is the reaction order with respect to B)

Overall order = x + y

Rate Constant
- related to how fast a reaction proceeds at a fixed temperature
 - changes with temperature
- determines the way the reaction rate varies with temperature (Arrhenius equation)

Reaction Orders

E.g. (CH3)3CBr(aq) + H2O → (CH3)COH(aq) + HBr(aq)

Δ [ ( CH 3 )3 CBr ] y
Rate ¿− =k [ CH 3 )3 CBr ¿ ¿ x [ H 2 O ]
Δt
The experiment determined rate law is:

0
Rate = [ CH 3 )3 CBr ¿ ¿ [ H 2 O ]
1

Reaction is said to be:

first-order with respect to (CH3)3CBr

zero-order with respect to H2O

Overall order = 1 + 0 = 1 (first)

This says:
 increasing the = [ CH 3 )3 CBr ¿ ¿ by z times increases the rate by z times
 changing the [H2O] does not affect the reaction rate

Hence, in a first-order process, the rate is directly proportional to the change in that reactant’s
concentration

In a zero-order process, the rate is not affected by change in that reactant’s concentration

E.g. 1 Consider the equation

5Br- + BrO3- + 6H+ → 3Br2 + 3H2O

Which is a correct expression of the rate of reaction of BrO3-

Δ [ H2O ]
a) b) Δ ¿ ¿ c) −5 Δ ¿ ¿ d) −0.2 Δ ¿ ¿
Δt

a) wrong because there are 3 H2O for every BrO3-

b) wrong because the rate of BrO3- is not equal to 3 times itself
c) wrong because Br- reacts with 5 times as frequently as BrO3-, not the other way around
 1
d) correct because BrO3- reacts times as frequently as Br-
5

E.g. 2 Consider the reaction:

2NO(g) + Cl2 → 2NoCl(g)

Which of the following is or are required for a successful reaction between NO and Cl 2
molecules?
I correct orientation
II NO to Cl2 ratio of 2:1
III Sufficient collision energy

a) II only b) I and III only

b) II and III only d) all of I, II, and III

answer:
B: orientation and collision is needed for any reaction
however, reactants do not have to be present in a perfect ratio to react
i.e some reactants can exist in excess and the reaction will still occur

Arrhenius Equation
relates the rate constant to:
 molecules must collide to react
 collisions must have the correct orientation
 collisions must have enough energy

−E a
RT
k=Ae
where:
k = rate constant
A = frequency factor (describes collisions, and collision orientation)

− Ea

e = f = the fraction of collisions which have enough energy for reaction to

RT

occur

Ea = activation energy
R = gas constant = 8.314 J/mol/K
T = temperature (K)

Note: As Ea increases, f decreases

e.g. if f = 0.08, then for every 100 collisions, 8 have enough energy for a reaction to occur
E.g. The following data were measured for the reaction

2NO(g) + 2H2(g) → N2(g) + 2H2O(g)

Experiment [No]0 (M) [H2]0 (M) Initial rate

−3
1. 0.1 0.1 1.23 ×10
2. 0.1 0.2 2.46 ×10−3
−3
3. 0.2 0.1 4.92 ×10
x y
Rate = k [ NO ] [ H 2 ]

looking at 1. and 2., doubling the [H2] causes the rate to double

x y
1.23 ×10−3 =k [ 0.1 ] [ 0.1 ]

x y
2.46 ×10−3=k [ 0.1 ] [ 0.2 ]

x y x y
k [ 0.1 ] [ 0.2 ] =2 k [ 0.1 ] [ 0.1 ]

[ 0.2 ] y =2 [ 0.1 ] y
y
2 =2

y=1

∴ first-order with respect to H2

looking at 1. and 3., doubling the [NO] causes the rate to quadruple

x y
1.23 ×10−3 =k [ 0.1 ] [ 0.1 ]

x y
4.92 ×10−3=k [ 0.2 ] [ 0.1 ]

x y x y
k [ 0.2 ] [ 0.1 ] =4 k [ 0.1 ] [ 0.1 ]

[ 0.2 ] x =4 [ 0.1 ] x
 x
2 =4

x=2
∴ second order with respect to NO

∴ Rate = k[NO]2[H2]

Rate
k= 2
[ NO ] [H 2 ]
−3
1.23 × 10
Using 1. : k =
( 0.1 )2 (0.1)

¿ 1.2

Overall order =2 + 1 =3 (third-order)

mol L−1 s−1

Units = 2
( mol L−1 ) mol L−1
−1
s
¿ 2 −2
mol L
2 −2 −1
¿ L mol s

This is the third-order rate constant unit

Note: the constant unit will change depending on the degree of order

Integrated Rate Law

 the formula when you integrate a differential rate law

e.g. for a zero-order reaction: A → products

Δ[ A ] 0
Rate= =k [ A ] =k
Δt

Δ[ A ]
∫ Δt
dt=∫ −k dt

[ A ] t =−kt + [ A ] 0
Concentration of A at time t Initial concentration of A

e.g. A first-order reaction: A→ products

−Δ [ A ]
Rate= =k [ A ]
Δt

−1
Δ [ A ]=k Δ t
[A]

−1
∫ [ A ] Δ [ A ] =∫ k Δ t

−ln [ A ] t =kt +c

ln [ A ] t =−kt +c 1

when t = 0, [A]t = [A]0

∴ ln [ A ] 0=−k ( 0 )+ c1

c 1=ln [ A ]0

∴ ln [ A ]t =−kt+ ln [ A ]0
(first-order reaction)

Note: Rate law is experimentally determined

It can NOT be determined from stoichiometry

e.g. Second-order reaction: A→ products

−Δ [ A ] 2
Rate= =k [ A ]
Δt

Integrated rate law:

1 1
=kt +
[ A ]t [ A ]0
(second-order reaction)

Summary:

if plot of [reactant] over time is linear, zero-order

if plot of ln[reactant] over time is linear, first-order
if plot of [reactant]-1 over time is linear, second-order

Pseudo Rate Order

When some reactants are in high excess, reaction rate is primarily dependent on the
concentration of the limiting reagent

Hence, such a reaction may have a pseudo rate order’ which summarises reaction speed
+ ¿→3 Br 2(l)+ 3 H 2 O(l) ¿
−¿+6 H (aq) ¿
e.g. Reaction BrO−¿
¿ +5 Br(aq) ¿

R=−Δ¿ ¿

(found experimentally)

∴ is third-order

take ¿ and ¿] in large excess

then k ¿ remains relatively constant lets call it k’

'
∴ R=k ¿
↑
k’ is a pseudo first-order rate constant

Half-lives
- another approach to describing reaction rate

- based on time required for the concentration of a reactant to decrease to one-half, its
initial value

i.e. from [ A 0 ] to
[ A0]
2

- this period of time is denoted t 1

2

- for first-order reactions, half life is independent of initial concentration

 useful for carbon dating

t1 [ A ]0
Zero-order reactions: 2
=
2k
¿
¿
 ln 2
First-order reactions:t 1 = k
2
¿

1
Second-order reactions: t 1 =
2 k [ A ]0

Proof:

First order integrated rate law:

ln [ A ] t =−kt +ln [ A ] 0
1
when t=t 1 , [ A ] t = [ A ]0
2 2

∴ ln ( 12 [ A ] )=−k t + ln [ A ]
0 1
2
0

( )
1
[ A]
2 0
ln =−k t 1
[ A ]0 2

t 1=
2
−1
k
ln ()
1
2

t1 ln2
2
=
k
¿ which is independent of [A0]
¿

E.g. 1 The radioactive elements G and H have half-lives of 5 minutes and 15 minutes
respectively. An experiment starts with 4 times as many atoms of G as H. How long will it be
before the number of atoms of G euqlas the number of H atoms.
(radioactive decay follows first-order kinetics)

2
G: t 1 =5=ln k
2
2
¿> k=ln
5

−ln 2
∴ ln [ G ]t = t + ln [ G ] 0
5

ln [ G ] t − ln2 t+ ln(4 [ H ]0 )¿
=
¿ 5
 t1 ln 2
H: 2
=15=
k
¿
¿
−ln 2
∴ ln [ H ]t = t +ln [ H ]0
15

when [ G ] t= [ H ] t

−ln 2 −ln 2
t+ ln ( 4 [ H ]0 ) = + ln [ H ] 0
5 15

ln
( )
4 [ H ] 0 2 ln 2
[ H ]0
=
15
t

15 ln 4
t=
2 ln 2

¿ 15
∴ it takes 15 minutes

E.g. 2 The radioactive isotope 64Cu is used in studies of the genetic disease known as Wilson’s
disease. The isotope has a half-life of 12 hours. What fraction of 64Cu remains after 24 hours?

ln 2
t 1 =12=
2
k

ln 2
∴ k=
12

−ln2
∴ ln [ 64Cu ]t= t+ ln [ 64Cu ]0
12

−ln 2
when t=24 : ln [ Cu ]24 = ( 24 ) + ln [ 64Cu ] 0
64
12

ln
( [ 64Cu ]24
[ 64Cu ]0 )=−2 ln 2

[ 64Cu ]24 =e 2 ln2=0.25

[ 64Cu ]0
¿ 25 %
A reaction mechanism describes how individual atoms, ions or molecule interact to form
products

Most likely a complex series of reactions which take place in a step-wise fashion

Each individual reaction is called an elementary reaction

 generally involve 1,2 or 3 species

The mechanism of the reaction is the overall sequence of elementary reactions

The sum of the elementary reactions must give the balanced chemical equation for the overall
reaction

e.g. NO2 + CO → NO + CO2

has a proposed two step mechanism:

Elementary step 1: NO2 + NO2 → NO3 + NO (slow)

Elementary step 2: NO3 + CO → NO2 + CO2 (fast)

NO 3 is an intermediate species

Proposed mechanisms can be supported with experimental data

The molecularity of an elementary reaction is the number of molecules that collide during that
step of the mechanism

single reactant (in elementary step): step is unimolecular

two reactant molecules: bimolecular

three reactant molecules: termolecular

The order of an elementary reaction is the same as the molecularity

The rate law can be obtained from the elementary reactions => use the slow step

E.g. 1. The decomposition of N2O is believed to occur by a two-step mechanism:

N2O(g) → N2(g) + O(g) (slow)
N2O(g) + O(g) → N2(g) + O2(g) (fast)

a) write the equation for the overall reaction

b) write the rate law constant with the above mechanism
 a) N2O(g) + N2O(g) + O(g) → N2(g) + O(g) + N2(g) + O2(g)

2N2O(g) → 2N2(g) + O2(g)

b) Must use the slow reaction as it is rate determining

The slow step is unimolecular, ∴ order is 1
From slow step: Rate = k1[N2O]1

E.g. 2. You lead an interstellar expedition to a remote planet. The arrival of your spaceship
initiates a reaction causing the atmosphere to decompose by a first-order rate law with a half
life of 13 hours. Everyone will heave to leave by te time only 13% of the atmosphere remains.
How much time do you have until then.

t1
2
=
ln2
k
¿ and ln [ A ] t =−kt +ln [ A ] 0
¿

ln2 ln 2
13= =¿ k=
k 13

−ln 2
∴ ln [ A ]t = t +ln [ A ] 0
13

−ln2
when [ A ] t= t + ln [ A ]0
13

ln ( 100
13
[ A ] )= −ln2 t+ ln [ A ]
0
13 0

( )
13
[ A]
100 0 −ln 2
ln = t
[ A ]0 13

t=ln ( 100
13
)÷ −ln13 2
¿ 38.2641413 hours

¿ 38 hours , 15 minutes ,52 seconds (nearest second)

It is difficult to derive the rate law for a mechanism where an intermediate is a reactant in the
rate determining step
i.e. the first step is not the rate determining step
Mechanisms with fast initial step are described to have pre-equilibrium

E.g. 2NO(g) + Br2(g) → 2NOBr(g)

has an experimentally determined rate law of:

Rate = k[NO]2[Br]

one possible mechanism:

single-step termolecular:

NO(g) + NO(g) + Br2(g) → 2NOBr(g)

Unlikely

Alternative Mechanism

k1
Step 1: NO(g) + Br2(g) NOBr2(g) (fast and reversible => pre-equilibrium)
k-1
k2
Step 2: NOBr2(g) + NO(g) 2NOBr(g) (slow)
We need to use the slow reaction to determine the rate law. However, NOBr 2, a reactant in the
slow reaction is an intermediate.

Step 2 Rate law:

Rate = k2[NOBr2][NO]
↓
we need to remove this in order to find the rate law for the overall reaction

Step 1: Rate of forward reaction = rate of reverse reaction

k1
NO + Br2 NOBr2
k-1
∴ k 1 [ NO ][ Br ]=k−1 [ NOBr 2 ]

k 1 [ NO ] [Br ]
∴ [ NoBr 2 ] =
k −1

k 2 k 1 [ No ][ Br ] [ No]
∴ Rate=
k −1

2
k observed [ NO ] [ Br ]
 which is consistent with the experimentally determined rate law

Pre-equilibrium can not be achieved if k2 >> k-1

NOBr2 is converted into NOBr before it can be converted to NO and Br

Pre-equilibrium is established if k2 << k-1

Enzyme Kinetics

Enzymes are protein catalysts which speed up the rate of a chemical reaction

 do this by temporarily binding to the substrate which lowers the Ea

Effect of substrate concentration on enzyme activity (reaction rate):

Michaelis and Menten observed that:

 at very low [S], v ∝ [S] (first-order with respect to [S])

 at very high [S], v is zero-order with respect to [s]

They proposed a simple model to account for enzyme behaviour

k1 k2
E+S ES E+P
k-1
where E = enzyme, S = substrate, ES = enzyme substrate complex, P = products
and k1, k-1, k2 are rate constants for their respective reactions

This means ES complex has two possible fates:

1. dissociate into E and S with rate constant k-1

2. proceed to form a product, P with rate constant k2

(product can not revert back to substrate)
Rate of reaction often expressed as the velocity of reaction (v)

v is limited by step 2 ( ES → E + P)

v depends on two factors:

1. Rate constant (k2) for ES → E + P

2. [ES]

v = k2[ES] (slow)

2 Assumptions in Enzyme Kinetics:

1. [S] >> [E]

2. System is in steady-state:

rate of ES formation = rate of ES breakdown

i.e. [ES] is constant

Rate of formation of ES = k1[E][S]

Rate of breakdown of ES = k-1[ES] + k2[ES]

∴ k1[E][S] = k-1[ES] + k2[ES]

k 1 [ E ] [S ]
[ E ]=
k −1+ k 2

Michaelis constant:

k −1+ k 2
k M=
k1

[ E ] [ S]
∴ [ ES ] =
kM

k M is a pseudo equilibrium constant.

Presence of k2 precludes it from being a true equilibrium constant
 k M ≈ k eq if k−1 >k 2

[ E ] [S ]
k M= ES ⇌ E + S
[ES ]

larger k M → products favoured (less ES)

k M is a measure of the strength of the ES complex

High k M : weaker binding of E to S

Low k M : stronger binding of E to S

Michaelis Equation

V max [ S ]
V=
k M +[S ]

V max =k 2 [ ES]

occurs when [ES] is at its maximum

(enzyme is 100% bound to S)

∴ V max=k 2 [ E ]total

[ S]
∴ V =k 2 [ E ] total ×
k M +[S ]

V max is also called k catalytic

- maximum number of substrate molecules converted into product per enzyme per unit
of time

For “catalytic perfection”

- need large k catalytic

- need low k M (strong binding of E to S)

1
When V = V , k =[S ]
2 max M
At low [S] : ([S]<<k M )

k M +[S]≈ k M

V max [ S ]
∴V ≈
kM

∴ V ∝ [ S ] ∵ k M ∧V max are constants

∴ 1st order with respect to [S]

At high [S] : ([S]>>k M )

[ S ] + k M ≈ [S ]

V max [S]
∴V ≈
[ S]

V ≈ V max

∴ zero order with respect to [S]

Units for k M same as [S]

Linweaver-Burk equation

1 k M +[ S]
= (reciprocals of Michaelis equation)
V V max [S ]

is in the from:

y=mx+b
 1 kM 1
=
( ) +
1
v V max [ S ] V max
↓ ↓↓
variable constant constant

variable

1 1
∴ plot of vs. is linear
V [S]

kM 1
with shape = and y-intercept
V max V max

Potential Energy Diagrams

Topic 3: Organic Chemistry
Summary of Analytical Methods (from Chem 1)

 Elemental (CHNX) Analysis

determines ratio of atoms C, H, N and heteroatoms: O, F, Cl, Br, I, S, P
- results give %m of each element
- gives empirical formula

 Mass Spectrometry
measures mass of a molecule

 Electron Impact Mass Spectrometry

- Molecule bombarded with high energy electrons to form radical cations:
−¿¿
e
+¿¿
M M•
2 e−¿¿

- Some radical cations break into fragments

M +¿¿
•
+¿+n ¿
• m
(cation) (neutral radical)
+¿¿
- Results plot mass : charge ratio (m/z) values of m cations, and the frequency of each

 Ultraviolet/Visible (UV/Vis) Spectroscopy

Uses UV/visible light radiation to move electrons from the ground state to an excited
state
 - similar to AAS, but for organic compounds instead of ions
- good measure of the extent of conjugation as electrons in conjugated π -bonds can be
promoted easily

 Infrared (IR) Spectroscopy

- Uses infrared radiation to make bonds stretch and bend
- Reference table: (given in exams)

carbonyls (C=O) have strong stretching absorbance

NH and OH groups give broad stretching absorbance

Also review:
- mechanisms: curly arrows, fishhead arrow, electrophiles and nucleophiles
- alkenes

Nuclear Magnetic Resonance (NMR) Spectroscopy

- most powerful routine analytical method available
- similar to UV/Vis and IR spectroscopy, but instead uses radio waves
- radio waves cause nuclear magnetic resonance

- can be used to determine if a sample is pure

- graphed results of a substance can be compared to known graphs in order to identify

the substance

- works based on the property that certain nuclei (importantly 1H and 13C) are ‘magnetic’

 they have ‘spin’ due to an odd number of neutrons. Spin generates a magnetic field

In solution these atoms spin at random

When placed in a magnetic field, they can have two energy levels

The low energy level is when the atoms align with the applied magnetic field

The high energy level is when the atoms oppose with the applied magnetic field

When radio waves are applied, some atoms in the low energy state move into the high
energy state.
 The system is put in an ‘excited state’

When the radio waves are no longer applied, the ‘relaxation’ (transition from excited
state to ground state) produces radio waves, which are observed.
NMR on 1H:

1. Sample is dissolved in a deuterated solvent

-> a compound where one or more of its hydrogen
atoms
are replaced with 2H (deuterium)
-> this ensures the solvent does not produce a signal
and
interfere with the results

2. Solution is placed in an NMR tube

-> highly engineered glass tube

3. Placed in an NMR spectrometer, which has a very strong magnet

4. Sample is spun to make it more homogenous

5. Substance is irradiated with a pulse of radio waves

6. When the pulse is finished, the nuclei relax back into the low energy state by
emitting radio waves

7. Results are analysed based on mathematical manipulation known as Fourier

transformation

intensity
( ¿ number of nuclei ) : y-axis
integral area

is graphed against:

δ : chemical shift (ppm) : x-axis

↓
The information about the ‘chemical environment’ of the substance you are
looking at
under NMR spectroscopy

A reference compound: Tetramethylsilane (TMS, Si(CH 3)4)

has δ=0 ppm

Chemical shift ¿∨frequency ( examined substance signal )−frequency ( TMS signal )∨¿

Almost all H atoms have chemical shifts of 0-10ppm

 A very small amount of examined substance is dissolved in solution, because interaction
between like molecules of this substance should be minimised

Nuclear Magnetic Resonance Imaging (MRI)

- Used extensively in medicine
- Related to NMR spectroscopy
- Involves radiation detecting density of hydrogen atoms from water

E.g. of NMR spectroscopy results

Butylated hydroxytoluene

This used chloroform (CHCl3) as the solvent, which has a chemical shift of 7.25ppm

If TMS was used, a small peak would be seen at δ =0

The other 4 peaks correspond to the types of hydrogen within the molecule

Ratio of peaks:
1 : 2 : 3 : 18

The height of the peaks is proportional to the amount of each atom represented by the peaks
 Main Aspects of 1H NMR:

Observation
Number of signals
Position of signal (chemical shift)
Intensity (size of integral)
Peak shape (splitting/multiplicity)
Information
Number of H ‘environments’ on the molecule
Type of H environment
Number of H of each type
Number of H in the immediate environment

Number of signals

When looking at hydrogen environments, consider symmetry of molecules

one signal in 1H NMR two signals in 1H NMR

three signals in 1H NMR four signals in 1H NMR

E.g. How many signals would you expect to see in the 1H NMR spectrum of each of the
following compounds?

a) −Br b) c) d)

e) f) Cl Cl g) O h)
solution
a)

b)

c)

d)

e)

f)

g)

h)
Position of signal

The 5 main regions (given in exam)

Protons on Protons on Protons on Protons on Protons on

unsaturated C unsaturated C unsaturated C: saturated C saturated C:
next to an on aromatic Alkenes next to an CH, CH2, CH3
electronegative hydrocarbons electronegative carbon chains
group (e.g. O) group
e.g. aldehydes

Intensity
e.g. 1-3-5-trimethyl benzene

The ratio of the integrals is identical to the ratio of the number of each hydrogen type
 E.g. Estimate the ratio of the signal sizes and the chemical shifts for each of the
following compounds?

a) −Br b) c) d)

e) f) Cl Cl g) O h)

Solution

a) Ratio = 1
Chemical shift: between 3 and 4.5 ppm
b) Ratio = 1
Chemical shift: between 0 and 3 ppm
c) Ratio = 1
Chemical shift: between 6.5 and 8.5

d)
Ratio = 2:6 = 1:3
Chemical shift: between 0 and 3ppm
e)
Ratio = 1:9
Chemical shift: between 0 and 3ppm
f)
Ratio = 2:4 = 1:2
Chemical shift: one peak between 0 and 3ppm, one peak between 3
and 4.5
ppm
g)
Ratio = 4:6 = 2:3
Chemical shift: between 0 and 3ppm
h)
Ratio = 2:4:6 = 1:2:3
Chemical shift: between 0 and 3ppm

Peak Shape

The n+1 rule

Fine structure (splitting or multiplicity) arises from the H atoms on adjacent C atoms.

If a H atom has n equivalent H atoms on adjacent C atoms, its NMR resonance will
appear as a signal that is split into n+1 peaks.
The ratio of the heights of the peaks will follow binomial distribution:
1
1 1
1 2 1
1 3 3 1
1 4 6 4 1
1 5 10 10 5 1
⋮

E.g.

H has 3 H on adjacent C atoms, so produces 4 peaks

H has 2 H on adjacent C atoms, so produces 3 peaks

Why does this occur?

Coupling arises because the magnetic field of adjacent protons influences the field that
the proton experiences

Consider 1,1-dichloroethane (CHCl2CH3)

From n+1 rule, H forms a doublet

The H either adds to or subtracts from the field the H atoms experience:

↑ spectrometer field:
 two possible states for H: therefore H has two different ppm values in a 1:1 ratio, so
forms a doublet

Now consider H
By n+1 rule, H forms a quartet.

There are 3 H’s that can have an affect on the shielding. The possible permutations are:

↑ ↑↓ ↓ ↓↑
↑ ↑↑ ↑↓ ↑↓ ↑↓ ↓ ↓↓
↓ ↑↑ ↑↓ ↓

1 : 3 : 3 : 1

The ↑ ↑↓ and ↓ ↓↑ combintions are three times as common as ↑ ↑↑ and ↓ ↓↓, so the peaks
are produced in this ratio

E.g. How many signals would be expected in the 1H NMR spectrum of each of the
following compounds, and give the ratio of the signal sizes and the multiplicities

a) b) c)

Solution:

a)
2 signals, ratio = 6:4 = 3:2

b)
3 signals, ratio = 3:3:2

c)
3 signals, ratio = 6:3:1
Additive splitting patterns
When one splitting pattern is split again by hydrogens from a different environment

e.g. 1-methoxypropane

For H the 3 H atoms will influence quartet splitting while the 2 H atoms will influence
triplet splitting.

Hence each splitting from the triplet will be split into a quartet (or vice versa)

We call this a quartet of triplets or a triplet of quartets

13
C NMR

Very useful for determining structure, especially if lots of C-H bonds

More challenging than 1H NMR because:

- low proportion of 13C (1.1%) means sample has to be concentrated and/or
analysed for longer
- 13C nucleus 50 times less sensitive than 1H, meaning bigger machines are
required and longer times for better spectra
- carbon signals can be split by 1H
- not quantitative (cannot integrate signals)

Double bond equivalents

Number of multiple bonds (pi bonds) and/or rings

¿H ¿N ¿ X
Double bond equivalents = ¿ C− + − +1
2 2 2

(X = Halogen atoms)

E.g.
H2N
6 total

Molecular formula = C11H13N

 13 1 0
DBE’s = 11− + − +1=6 ✓
2 2 2
Functional group chemistry: Alcohols, Phenols and Ethers

Ether:

R−O−R

Phenol:

Alcohols

R = any substituent other than H

Naming Compounds
Recall:

parts of molecule not in stem the functional group

↓ ↓
Number(s) Substituents Stem Ending
↑ ↑
location of substituents number of carbons in the longest chain
containing the functional group

When naming alcohols, 2 possible scenarios:

If the alcohol group has priority over all other functional groups:
the stem must contain the O-H group and the ending is -ol
If the alcohol group does not have priority over all other functional groups:
name the O-H group as a hydroxy substituent
Alcohol
Ending = -ol, or there is a hydroxy substituent

Ether
Ending = ether or there is a alkoxy substituent

E.g. Classify the following alcohols as primary, secondary or tertiary:

a) b) c) d)

Solution:
a) secondary
b) primary
c) tertiary
d) secondary

Structure and Properties of Alcohols and Phenols

O is sp3 hybridised

O has 2 lone electron pairs

O-H bond is strongly polarised

(because O is more electronegative than H)

Form hydrogen bonds => high solubility in water, high melting/boiling points

Identifying Alcohols, Phenols and Ethers

1
H NMR
Alcohols and ethers: protons on C next to O will have higher ppm value (due to
electronegativity of O), usually around 3-4.5ppm

Phenols: Aromatic protons in 6.5-8.5 ppm range

Alcohols and phenols:

Broad 1H peak for OH proton due to H-bonding with residual water

Infrared spectroscopy
Alcohols and phenols: O-H stretch = 3200 – 3600 cm-1
Phenols: C=C stretch (aromatic) = 1400 – 1600 cm -1
Ethers: C-O stretch = 1000 – 1300 cm-1
UV/Vis
Phenols: absorbs in the UB/vis due to aromatic ring

Acid-Base Reactions:

Least acidic →Most acidic:

alcohols < water < phenol < carboxylic acids

Alcohols
+ ¿¿

R−OH ⇌ R−O−¿+H O 3 ¿

↑
alkoxide ion

k a=¿ ¿

p k a =−log 10 k a

Phenol:
−¿+ H 2 O ¿

−OH + OH −¿ ⇌−O ¿

↑
phenoxide ion

Phenoxide ions are easier to form than alkoxide ions

This is because phenoxide ions are more stable, due to delocalisation of electrons

The negative charge is not exclusively centred on the oxygen (as in the case with alkoxides) but
is shared with three of the six carbons on the benzene ring
Resonance hybrid:

[
]
Carboxylic Acids>

⇌ - + H+
↑
Carboxylate anion

Stability of carboxylate anion:

negative charge is shared between the two oxygens

Sodium alkoxides can be prepared by the reaction of alcohols with sodium metal

Na +¿¿
1
−¿+ H 2 ¿
2
R−OH + Na→ R−O

Sodium carboxylates can be made by the reaction of carboxylic acids with the weal base sodium
hydrogen carbonate

−¿→¿

+ Na
+¿ HCO3 ¿
+ Na+¿+CO +H
2 2 O¿
-

Carboxylic acids are more acidic so form salts more readily. Hence they can react with weak
bases
Types of reaction revision:

Addition: loss of multiple bond, formation of one product

Elimination: formation of multiple bond, 2 molecules formed

Substitution: substituent is swapped

Preparation of Alcohols

1. Acid catalysed electrophilic addition of water to alkenes (hydration)

(dilute H2SO4)
e.g. H2SO4, H2O
+
major product minor product

Markovnikov’s Rule: the H of the reagent goes to the C with the most H’s, more often

+¿¿ HH
+¿¿
H OH 2 H OH 2 O+¿¿ OH
+¿ ¿
+H
H H

Major product
HH
H H
+¿¿
H OH 2 +¿¿ OH 2 +¿O ¿ OH + H +¿¿
+¿¿
H H
Minor product
Reactions of Alcohols

conc. H2SO4
Alcohol Alkene + H2O

Classification of Reactions by Mechanism:

Organic reactions are classified by what happens and how they happen

1. Overall type of process:

addition (A), substitution (S), elimation (E)

2. Nature of the reagent which first interacts with the organic substrate ( N or E)
 3. The type of substrate or the number of molecules involved (not always needed)

A: π -bond broken
E: π -bond formed
S: substituent is replaced

Dehydration of alcohols is an ‘E1 mechanism’ (unimolecular elimination)

 Only one molecule, and a π bond is formed

e.g.

Zaitsev’s rule: the most substituted (less H) will be most stable and hence most favoured

1° alcohols don’t dehydrate easily because the carbocation formed is very unstable

Carbocation stability:

> > >

3° 2° 1°
most stable least stable
Substitution Reactions (SN1)
-> unimolecular nucleophilic substitution

H HH
O H +¿¿ +¿¿ O −HO H R ' +¿ R ¿ X −¿¿ X
R
' '
R RRR RRR R' R
3° or 2° alcohols oxonium ion carbocation alkyl halide

R’ = R or H

Strong acids are needed

 HCl, HBr, HI

e.g.

SN1:

SN2:

Substitution Reactions (SN2)

H HH
O H +¿¿ +¿¿ O X −¿¿ X
−HO H H
' '
R R H R R H R' R
1° or 2° alcohols oxonium ion alkyl halide

carbocation is too unstable to form

Oxidation of Alcohols
we do not need to know mechanism
we just need to know:
many reagents can oxidise alcohols
such as dichromate ion in acid

Oxidation of primary alcohols forms carboxylic acids

[ ]
OH O
+¿ ¿
2−¿/ H ¿
Cr 2 O
7 O
oxidation oxidation
RHH RH R OH
aldehyde carboxylic acid
(not isolated)

Oxidation of secondary alcohols forms ketones

OH O
+¿ ¿
2−¿/ H ¿
Cr 2 O
7
oxidation
RRH RR
ketone

tertiary alcohols: no reaction

 because reation requires hydrogens to be replaced

Old breathalisers based on colour change associated with such reactions

Oxidation of alcohol in body is catalysed by alcohol dehydrogenase

CH3CH2OH → CH3CH=O → CH3CO2H

(ethanol) (acetic acid)

CH3OH → H2C=O → HCO2H

(methanol) (formic acid)
-> damages body

E.g. What reagents are required for the following transformations?

a)

b)
c)

d)

Solution:

a) 2° alcohol
Nucleophilic substitution
∴ S N 1∨S N 2
reagent: HBr

b) 2° alcohol
Elimination reaction, E1
reagent: concentrated H2SO4

c) strong reagent needed since alcohols are very weak acids

∴ reagent: Na

d) 2° alcohol (2° oxidation → ketone)

∴ reagent: Cr2O72-/H+

Alkyl Halides and Aryl Halides

Alkyl Halide
A hydrocarbon containing a halogen atom

R
R C X
R X = F, Cl, Br, I
- can be primary, secondary or tertiary

Aryl Halide

Nomenclature:

2 scenarios:
 - haloalkane – fluoro, chloro, bromo, iodo

- alkyl or aryl halide – fluride, chloride, bromide, iodide

Alkyl halides are dense gases, liquids and solids, which are insoluble in water
 because halogens are dense

Slight dipole between C and X is not strong enough to disrupt hydrogen bonding of water
 hence insoluble

Identifying Alkyl Halides

1
H NMR
Protons on carbon next to halide will have higher ppm (due to electronegativity of halide),
usually around 3-4.5 ppm

Infrared Spectroscopy

C-F, C-Cl, C-Br, C-I all absorb in the fingerprint region

Mass Spectrometry

MOST USEFUL

Characteristic isotope patterns:

35
Cl = 75% abundance
37
Cl = 25% abundance

79
Br = 50% abundance
81
Br = 50% abundance

Uses of Alkyl Halides

Carbon fluorine compounds very inert

Polytetrafluoroethylene
(teflon)
  Used on frying pans, and medical applications

Polyvinyl Chloride

polymer used in pipes

DDT
antimalarial pesticide

Agent orange
used in chemical warfare

CFCs (chlorofluorocarbons)

Halothane
anesthetic

Perfluorodecalin
Artificial blood
Designed to combat AIDS
Has effective oxygen transport capability

Preparation of Alkyl and Aryl Halides:

1. Electrophilic addition to alkenes (X2 or HX)

e.g.
 2. Nucleophilic Substitution of alcohols (conc. HX)

e.g.

3. Electrophilic Aromatic Substitution (X2, Lewis acid catalyst)

e.g.

 known as bromination

Bromination Mechanism

Reactivity of Alkyl Halides

Reactivity is dominated by the attack of nucleophiles at the carbon atom which is bonded to the
halogen atom: nucleophilic substitution

−¿+H 3 C− X → Nu−CH 3 +X ¿
Nu
OR
−¿ ¿
+¿−CH 3 +X ¿
Nu+ H 3 C− X → Nu
 SN1 Nucleophilic Substitution of Alkyl Halides

slow, rate determining step

(unimolecular)

fast fast

planar carbocation
intermediate leaving group

The greater the number of substituents around the carbon centre undergoing reaction, the
more stable the carbocation, and hence the faster the reaction

methyl halide 1° alkyl halide 2° alkyl halide 3° alkyl halide

H R R R

H X H X R X R X
H H H R
slow fast
H R R R
 H H H H R H R R

methyl carbo cation 1 ° carbocation 2° carbocation 3° carbocation

least stable most stable

Stereochemical Outcome:

Products will always be 50% of each

Stereoisomer (due to planar shape of carbocation)

The stereogenic information of the original molecule is lost

SN2 Nucleophilic Substitution of Alkyl Halides

Direct single step substitution of an alkyl halide by a nucleophile with no intermediates

E.g.

H3CH2C 1 CH2CH1
3
2
−¿¿ CH2CH3
−¿ ¿
2
CH3 +¿¿
Br H3 C Br CH3 Br−¿¿
δ δ −¿¿
Nucleophile
CH3 CH3 CH3
Electrophile Product
Transition state

As number of substituents around the carbon centre undergoing reaction increases, the
substituents block the approach of the incoming nucleophile, causing the S N2 reaction to
become slower

Stereochemical outcome:

Overall inversion of the stereochemistry

SN1 and SN2 rates:

SN1 rate increases

methyl halide 1° alkyl halide 2° alkyl halide 3° alkyl halide

 SN2 rate increases

SN2:

aromatic ring completely blocks attack of nucleophile

Nu¨ ¿
−¿
−Br

SN1:

sp2 carbocation too unstable for aromatic rings

Summary of SN1 and SN2 Mechanisms

SN1 SN2
Substitution, nucleophilic, unimolecular Substitution, nucleophilic, bimolecular

Rate = k[alkyl halide] Rate = k[alkyl halide][nucleophile]

2 steps, involves a carbocation intermediate 1 step, no intermediate

Reaction rate only determined by Reaction rate determined by [electrophile]

[electrophile] and [nucleophile]

Chiral compounds => racemisation Chiral compounds => inversion

Rate increases with degree Rate decreases as degree increases

Usually only 3° alkyl halides Usually only methyl, 1° and 2° alkyl halides

Aryl halides do not react Aryl halides do not react

Mustard gas
- Used in WW1
- SN2 – like mechanism

Nu
Nu-

Nu Nu

It can bind to proteins, enzymes and DNA

Fritz Haber
- developed mustard gas
- Nobel prize for synthesis of ammonia from its elements

Victor Grignard
- developed phosgene
- Nobel prize for discovery of Grignard reagent

With alcohols, you have complete substitution and elimination

With halides you have the same competition

e.g. Increasing [NaI] increases rate of reaction

This tells us it is SN2

If this product is treated with KOH, you get:

Which is an elimination mechanism

Alkyl halides undergo elimination reactions to form alkenes

HX is eliminated

e.g

MAJOR: most substituted alkene

MINOR

Mechanism for alcohol → alkene: E1

carbocation

oxonium ion

major product

E2 not possible with alcohols, because if base is involved with reaction, instead of pulling off a
blue or green hydrogen, it will pull a hydrogen off the oxonium ion, taking it back to the starting
material.
Mechanisms for alkyl halides:
General E1 mechanism for alkyl halides:
−¿ ¿
E1: B = base

rate determining
step
(unimolecular)

rate = k[alkyl halide]

Solvent molecules are basic enough to remove proton from carbocation (hence don’t need a
B−¿ ¿ drawn in mechanism)

For E1 to proceed, carbocation intermediate must be relatively stable

(1° alkyl halides can not undergo E1)

Nature of base does not impact E1

E2 Mechanism:

General E2 mechanism for alkyl halides

rate determining
step
(bimolecular)

rate = k[alkyl halide][B-]

For E2, rate of reaction depends on both [alkyl halide] and [base]
Stronger bases favour E2 mechanisms

- Most eliminations of alkyl halides are E2

E.g. Draw a mechanisms for the following reaction and classify the reaction type

various bases

Solution:
Reaction is dependent on bases. Therefore it is E2.

 E1 is a two-step mechanism

 E2 is a one-step mechanism

Grignard Reagents
- Formed via reaction between magnesium in dry ether solvent with alkyl or aryl halides
- Is an organometallic compound
-> contains carbon bonded to a metal
- A useful intermediate in the synthesis of alcohols and carboxylic acids

E.g.
This is a redox reaction:

A Grignard reagent can be thought of as containing:

a polar covalent C-Mg bond

OR

an ion pair

Due to differences in electronegativity: X highest, then C, then Mg:

C−Br and C−Mg

−¿¿ +¿¿

δ +¿δ ¿ δ −¿ δ ¿

are both polar

Alkyl Grignards Aryl Grignards

sp3 hybridised sp2 hybridised

=> tetrahedral => trigonal planar

* Grignard reagents can be used to make C-C bonds

 Very useful in synthesising organic compounds

Amines

R, R’, R” = alkyl, aryl or H

Lone pair of electrons
 mainly act as nucleophiles/bases

Primary (1° ) amine:

no more than one non-H substituent

e.g. methylamine

Secondary (2° ) amine:

2 non-H substituents

e.g. dimethylamine

Tertiary (3° ) amine:

3 non-H substituents

e.g trimethylamine

Quaternary Ammonium Halide Salt

4 substituents

e.g. tetramethylammonium chloride

Aromatic Amines

e.g. 4-bromoaniline

(primary)

Nomenclature

aminoalkane OR alkyl/aryl amine

Structure and Properties

Primary and secondary amines have hydrogen bonding due to N-H bond
 higher boiling point

Smaller amines are solluble in water

H-bonds from amines are responsible for complementary base pairing of DNA

Purine Pyrimidine

Purine Pyrimidine

Identifying Amines

1
H NMR
protons on C next to N have higher ppm (3-4.5) due to electronegativity of nitrogen

- Broad 1H peak for N-H protons in primary or secondary amines, due to H-bonding with
water

Infrared spectroscopy
N-H stretch 3200-3500 (weak)
C-N stretch 1080-1360 (weak)
N-H bend ~1600
Elemental analysis
can calculate % of N

Acid-Base Reactions
Amines are weak organic bases
−¿¿
+¿+OH ¿
R−N̈ H 2 + H 2 O⇌ R−NH 3

The higher the pKa of the conjugate acid, the more basic the amine

Alkyl groups increase basicity

Arene groups decrease basicity

Non-water soluble amines can be made more solluble by formign ammonium ions

Amines as Nucleophiles

Amines can react as nucleophiles with 1° or 2° alkyl halide electrophiles, in a nucleophilic

substitution reaction

A 3° amine reacts with an alkyl halide to form a quaternary ammonium ion

e.g. ¿
−¿¿
+ ¿N −+I ¿
− N̈−+−I →
¿ /¿

SN 2
1° amine R N̈ H 2+ R−X → 2° amine
¿
SN 2
2° amine R2 N̈ H + R−X → 3° amine
¿
SN 2
3° amine R3 N̈ + R− X → quaternary ammonium salt
¿

Cocaine and caffeine are amines

NaOH
Cocaine “crack” cocaine + NaCl + H2O
acid-base reaction
ammonium chloride 3° amine
salt

higher m.p lower m.p. →vaporises more easily

-> can be inhaled
higher H2O solubility lower H2O solubility
-> can not be administered via injection

no Et2O solubility soluble in Et2O

Other biologically active amines:

amphetamine, MDMA, methamphetamine, nicotine, morphine

Aldehydes and Ketons

contain a C=O bond

C of C=O is sp2 hybridised

ketone:

aldehyde:

simplest member:
formaldehyde:

High bond angle gives reagents easy access to the C=O carbon

C=O bond is polarised by electronegative O

This makes the carbon electrophilic, and hence susceptible to nucleophiles

Identifying Aldehydes and Ketons

1
H NMR:
Protons on C net to carbonyl (C=O) have higher ppm due to electron withdrawing nature of
carbonyl, usually around 2.5-3
- Aldehydes only: peak at 8-11 ppm for proton on C=O carbon

UV/Vis spectroscopy:
No intense absorption
Conjugated carbonyls have absorption

Infrared spectroscopy
** good for quick identification of carbonyl **

Aldehyde C=O stretch 1720-1740

Ketone C=O stretch 1705-1725

Nomenclature

ending is -al for aldehyde, one for ketone

OR

called aldehyde or ketone

e.g.s:

methanal ethanal propanal

(formaldehyde) (acetaldehyde) (propionaldehyde)

propane benzaldehyde acetephenone

(acetone)

Remember, alcohols can be oxidised to form aldehydes and carboxylic acids, or ketones, with
dichromate ion in acid: (Cr2O72-/H+)
 Cr2O72-/H+ Cr2O72-/H+
1° alcohols aldehydes carboxylic acids
oxidation oxidation

Cr2O72-/H+
2° alcohols ketones
oxidation

(Tertiary alcohols can not be oxidised)

Hence, aldehydes can oxidise, while ketones can not

Aldehydes and ketones undergo:

Nucleophilic addition reactions

- carbonyl group is strongly polarised
+¿¿
- carbonyl carbon has partial positive charge (δ ) so is electrophilic

- carbonyl group is unsaturated so undergoes addition reactions

- large bond angle → carbonyl carbon vulnerable

Undergoes nucleophilic attack

General Mechanism:

nucleophilic acid-base
addition reaction
nucleophile electrophile alkoxide anion an alcohol

2 steps:
 nucleophile adds to aldehyde/ketone
 alkoxide reacts with aqueous acid

How can this be used to out advantage?

This process allows us to make new C-C and C-H bonds
 both transform carbonyl functional group into an alcohol

C-C bonds: require carbon nucleophile => Grignard reagent

 nucleophilic addition
followed by acidic
work up
carbon
nucleophile

C-H bonds: require a hydrogen nucleophile (hydride)

−¿ ¿
H from NaBH4 or LiAlH4

nucleophilic addition
followed by acidic
work up
hydrogen
nucleophile

C-C bonds mechanism:

carbon nucleophile

nucleophilic
addition
Grignard alkoxide anion
reagent
acid-base
reaction

alcohol

C-H bonds mechanism:

nucleophilic
addition
acid-base
 reaction

Forming C-O bonds:

aldehyde/ketone alcohol hemiacetal

Equilibrium favours hemiacetal when alcohol and aldehyde/ketone are in the same molecule

(catalysed by acid)

alcohol aldehyde hemiacetal

functional group functional functional group
group

E.g.s of biologically active compounds containing aldehydes or ketones

-> typically have characteristic smells
-> related to interaction with receptors

- cinnamaldehyde: characteristic smell of cinnamon

- citronellal: in mosquito repellant candle

- retinal: basis for vision, conjugated molecule, so interacts with visible light

- testosterone: male growth hormone, produced from progesterone

- progesterone: female growth hormone

Carboxylic Acids

Structure

e.g. formic acid in ant venom

e.g. acetic acid vinegar

Nomenclature (recognising names, not naming complex structures)

ending is -oic or -ic acid for carboxylic acid

ending is -oate or -ate for carboxylate anion (conjugate base of carboxylic acid)

e.g.

methanoic acid methanoate

(formic acid) (formate)

Carboxylic acid

Ethanoic acid Propanoic acid Butanoic acid Benzoic acid

(acetic acid) (propionic acid) (butyric acid)
Carboxylate
anion

Ethanoate Propanoate Butanoate Benzoate

(Acetate) (propionate) (butyrate)
Acyl Substituent
Ethanoyl Propanoyl Butanoyl Benzoyl
(acetyl) (propionyl) (butyryl)
Identifying Carboxylic Acids

1
H NMR:
Protons on carbon next to carbonyl will have higher ppm due to electron withdrawing nature of
carbonyl (2.5-3.0 ppm)

UV/Vis Spectroscopy:
Conjugated carbonyls

Infrared Spectroscopy:
Most useful due to O-H stretch and C=O stretch

C=O stretch 1720-1740

O-H stretch 2500-3300 (broad)

Acid base reactions

More acidic than: phenol, water, alcohol

because:
carboxylate anions are more stable than alkoxide anions, and phenoxide anions due to
resonance

phenoxide anion has 4 resonance

contributors, but only one doesn’t
dirsupt formation of aromatic ring

hence net result is less favourable

Hydrogen bonding

Carboxylic acids can form dimers via hydrogen bonding

 increased boiling point

 greater solubility in water

Formation of Carboxylic Acids:

- Oxidation of alcohols/aldehydes

- Forming C-C bonds with Grignard reagents and CO2

nucleophilic
addition
Grignard reagent carbon dioxide
(electrophile) acid-base
reaction

carboxylic acid

Carboxylic Acid Derivatives

have an acyl group attached to a heteroatom
 OH is substituted

carboxylic acyl chloride acid anhydride ester amide

acid

Hydrolysis of Carboxylic Acid Derivatives

Hydrolysis of a carboxylic acid derivative forms the corresponding carboxylic acid

acyl chlorides H2 O
hydrolysis hydrochloric acid
acid anhydrides H2 O
hydrolysis carboxylic acid

esters H2 O
hydrolysis alcohol

amides H2 O
hydrolysis amine

Mechanism:

nucleophilic
addition
water tetrahedral intermediate
acyl chloride (nucleophile) (acts as an acid)
(electrophile)
acid-base
reaction

elimination
carboxylic hydrochloric (E2)
acid acid

Relative Reactivity of Carboxylic Acid Derivatives

acyl chloride acid anhydride ester amide

Explanation:

The more electronegative the substituent, the greater the partial positive charge on the carbon
atom of the carbonyl group and therefore the more electrophilic (reactive)

Resonance stabilisation due to lone paris of heteroatoms can contribute to stability → less
reactive

Why amides are stable:

resonance forms resonance hybrid

Base hydrolysis (of esters)

When a base is a better nucleophile than water, so can undergo nucleophilic addition with a
carboxylic acid derivative (instead of water)

Acidic hydrolysis (of esters)

Carboxylic acid derivative (ester) undergoes acid base reaction (acts as a base and is protinated)
before nucleophilic addition with water.
This makes the ester a better electrophile, and causes a better leaving group to be formed:
 water

nucleophilic
acid-base addition
ester reaction
protonated ester
(better electrophile) acid-base
reaction
better leaving group

elimination acid-base
reaction

acid-base
reaction

Formation of Acid Chlorides

treatment of a carboxylic acid with thionyl chloride (SOCl 2)

Carboxylic acid thionyl chloride acyl chloride sulfur dioxide

Summary of Preparation of Carboxylic Acid Derivatives

SOCl2 (thionyl chloride) acyl chloride

−HCl ,−SO 2

carboxylic
acid

R’OH −HCl R’R”NH

−¿¿
carboxylate −Cl alcohol amine
−HCl

acid anhydride

ester amide

Unifying Concepts
Esters:
associated with fruity smells

Amides
 make up proteins

Summary
* = must know mechanism
* = just know reaction

Phenols
(1) Undergo: acid base reactions → phenoxide ion
* (resonance)

Alcohols
(3) Formed by: - electrophilic addition of water to alkenes (with dilute H2SO4) *(major and minor)
- SN1, SN2 of alkyl halides *
- nucleophilic addition and acid base reaction of Grignard reagents with
aldehydes/ketones *

(6) Undergo: - dehydration * (E1), (with concentrated H2SO4) to form alkenes

- SN1 * (3° or 2° ) to form alkyl halide
- SN2 * (1° or 2° ) to form alkyl halide
- oxidation *, with dichromate ion in acid (Cr2O72-/H+)
→primary → aldehyde, secondary → ketones
- acid-base with Na → alkoxide ion *
- nucleophilic addition with aldehyde → hemiacetal

Alkyl Halides

(2) Formed by: - nucleophilic substitution of alcohols *

- electrophilic * addition of halogen (X2) or hydrogen halide (HX) to alkenes

(5) Undergo: - SN1 *, produces mixture, fastest to slowest: 3° , 2° ,1° alcohol

- SN2 *, inverts stereochemistry, fastest to slowest: 1 °,2° ,3°
- Elimination (E1 and E2) → alkenes *
- Mg in dry ether solvent → Grignard reagent *
- Nucleophilic substitution with amines (SN2)

Aryl Halides

(1) Formed by: - electrophilic aromatic substitution * with halogen molecule and Lewis acid
catalyst
(1) Undergo: - reaction with Mg in dry ether solvent -> Grignard reagent *

Amines
(3) Undergo: - reaction with acyl chloride to form amide
- acid-base reactions *
- SN2 with alkyl halide and acid base reaction *
1° →2 ° → 3 ° → quaternary ammonium salt

Aldehyde
(1) Formed by: - oxidation of 1° alcohol *
(3) Undergo: - oxidation → carboxylic acid *
- nucleophilic addition → alcohols *
-> C nucleophile → C-C bond, H nucleophile → C-H bond *
- nucleophilic addition with alcohols → (C-O bond): hemiacetal *

Ketone
(1) Formed by: - oxidation of 2° alcohol *
(2) Undergo: see above *

Carboxylic Acid
(3) Formed by: - oxidation of aldehydes *
- Grignard + CO2 *
- hydrolysis of carboxylic acid derivatives *
(2) Undergo: - acid base reaction → carboxylate ion * (resonance)
- thionyl chloride → acyl chloride *

Carboxylic Acid Derivatives

thionyl chloride *
(1/2) Formed by: carboxylic acid acyl chloride
carboxylate alcohol amine
acid anhydride ester amide
* (resonance)
(1) Undergo: - hydrolysis → carboxylic acids *
Summary of Reactions & Mechanisms

Phenol Acid-Base Reaction (formation of phenoxide ion)

Resonance of Phenoxide Ion

Carboxylic Acids Acid-Base Reaction (formation of carboxylate ion)

Resonance of Carboxylate Ion

Alcohol Acid-Base Reaction (formation of alkoxide ion)

Acid Catalysed Electrophilic Addition of Water to Alkenes (hydration) to form alcohols

- Major product:

- Minor product:

Dehydration (E1) of Alcohols

- Formation of Carbocation:

- Major product:

- Minor product:
SN1 of Alcohols

SN2 of Alcohols

Oxidation of Primary Alcohols

Oxidation of Secondary Alcohols

Oxidation of methanol and ethanol in the body

Electrophilic Addition of Alkenes

Bromination (electrophilic aromatic substitution)

SN1 of Alkyl Halides

SN2 of Alkyl Halides

Mustard Gas Mechanism

E1 of Alkyl Halides

E2 of Alkyl Halides
Formation of a Grignard Reagent

- Overall

- Redox

Acid-Base Reactions of Amines

SN2 of Amines

- 1° amine:
 - 2° amine:

- 3° amine:

Nucleophilic Addition of Aldehydes and Ketones

Formation of Carboxylic Acid with Grignard reagent and CO2

Hydrolysis of Carboxylic Acid Derivatives

Resonance of Amides

Formation of Acid Chlorides

Preparation of Carboxylic Acid Derivatives from Acid Chloride

- Acid Anhydride:

- Ester:

- Amide:
 base Summary of Reaction Types
Phenol hydrolysis
Phenoxide ion Carboxylic
acid derivative Grignard
CO2
reagent
base
Nucleophilic addition
Carboxylic acid
Alkoxide Ions Carboxylate
oxidation
ion
Na
*oxidation
Aldehydes
1° Alcohol Nucleophilic addition
*oxidation
Alcohols 2° Alcohol Ketones

3° Alcohol
dehydration
(E1) SN2 SN1 SN2
SN1
SN1 *: Cr2O72-/H+
Alkyl Halide S N2
hydration
(electrophilic
addition)
electrophilic aromatic
Alkenes electrophilic Aromatic substitution Aryl
addition E1 Halide
compound
E2
Topic 4: Inorganic Chemistry
What is inorganic chemistry?

Definition: deals with inorganic compounds, is literally “non-organic” chemistry

In practice: chemistry of elements that are not C, H, N, O

However, line gets very blurry on what constitutes an organic vs inorganic molecule

3 main groups of elements in inorganic chemistry:

 Transition metals

 Lanthanides / Actinides

 Main group
(everything else)

Periodic Trends:
↑ ionisation energy, ↓ atomic radius, ↑ electronegativity, ↓ metallic character
↓ ionisation energy, ↑
↓ electronegativity, ↑

Effective nuclear charge (Zeff)

The net positive charge experienced by an electron in a polyelectronic atom
- influenced by number of protons

- increases across and down periodic table

↓
more significant influence
  across: more protons, electron shielding remains constant
 down: more protons being added

Radii

Atomic radius
distance from centre of atom to edge
- location of edge is hard to define

Metallic radius Covalent radius Ionic radius

Atomic radius trends:

Across period: decreases due to increasing Zeff

Down group: increases as electrons are being put into orbitals with higher n

~ Transition metals do not entirely follow these trends

Ionic Radii

- Cation ions radii are smaller than the atom’s radii

 because less electrons means each electron experiences greater positive charge

- Anion ions radii are larger than the atom’s radii

 because more electrons means less positive charge experienced by each electron

Trends:
Across period:
Varies, since different ions are formed (different ± and different coefficients to the charges)
Down group:
generally, ionic radius increases down a group due to electrons being put into higher orbitals

E.g. Which is the largest of the following and which is the smallest?

O, O2-, S, S2-
Solution:

S if further down than O, so S > O

O2- is an anion so O2- > O
S2- is an anion so S2- > S

∴ S2- > S > O

O2- > O

S2- is biggest, O is smallest

Ionisation Energy
The energy required to remove 1 mole of e- from 1 mole of a gaseous element.
These values are always positive as ionisation can not occur spotaneously.

- Increases across a period

- Decreases down a group

Notation:
I1 = Cl(g) → Cl+(g) + e-
I2 = Cl+(g) → Cl2+(g) + e-
I3 = Cl2+(g) → Cl3+(g) + e-
⋮

I1 < I2 < I3 < ...

Electron Affinities
Measure of how readily a substance will accept an electron
- Sort of the opposite of ionisation energy
- A measure of how favourable the reaction of accepting electrons is
- Can be (-) or (+)
- If (+), value is unknown
- The value is the amount of energy absorbed ( (-) means energy is released)
- More negative = more favourable

E.g. Why do group 1 metals all have favourable electron affinities while group 2 metals don’t?

Group 2 metals already have a filled s subshell so requires the higher energy p orbital to be
filled, which is unfavourable

Group 1 metals are able to pick up electrons to fill s orbitals

 - Electron affinities generally become more favourable (negative) across a period
 not true for group 15, which have one electron in each of the three p orbitals.
Adding an electron causes pairing, which is not as favourable.

 Noble gases always have positive electron affinities:

Unreactive: do not want to give electrons due to high ionisation energy, do not want
to accept electrons as that requires placing them in a higher energy level
(new period)

Metallic Character

Properties of metals
- shiny, malleable, ductile, conductor of heat, conductor of electricity, form cations in
solution -> easily oxidised -> allows for metallic bonding which requires a sea of
delocalised electrons

- conversely, non-metals tend to be easily reduced

- metal oxides are basic

 e.g. reacting a metal with oxygen (usually by burning) will give an oxide:

4Na(s) + O2(g) → 2Na2O(s)

2Na2O(s) + H2O(l) → 2NaOH(aq)

Group 1 Metals
low ionisation energy, easily oxidised: (low E° , ~3V)
 vigorously by water, and by oxygen

e.g. 2Na(s) + 2H2O(l) → 2Na+(aq) + 2OH-(aq) + H2(g)

- one valence electron -> metallic bonds relatively weak

 lower melting point

Group 2 Metals
E° ~-2 −¿ -2.8

Generally oxidised by water

e.g. Ca(s) + 2H2O(l) → Ca2+(aq) + 2OH-(aq) + H2(g)

Be no reaction
Mg reaction with steam
Ca
Sr reaction with cold water
Ba

Both group 1 and 2 metals get more reactive down the group

Group 13
Boron: a metalloid: some metallic properties, some non-metallic properties

Aluminium: has some slight metalloid tendencies but is still a metal

⋮ rest of group 13 are also metals

Group 14
Carbon: non-metal, but has some metalloid tendencies
-> conducts heat and electricity (as graphite)

Silicon, Germanium: metalloids

Tin, Lead, Flerovium: metals

Groups 15 & 16
Similar trends, metallic character increases as you go down each group

Group 17 (Halogens)
All non-metals
F
Cl
Br
I
At

- very hard to remove electrons

- very easy to add electrons

very hard to oxidise halogens, but halogens are good at oxidising

- Reduction potential decreases down the group

Group 18: The noble gases

- Both very hard to add and remove electrons

- Originally thought it was impossible for noble gasses to form compounds

- Neil Bartlett
Showed ionic compounds could be made with nobel gases
o Used PtF6, an extremely potent oxidising agent which readily picks up electron to
form PtF6-
↓
Reacted with xenon

Xe + PtF6 → Xe+[PtF6-]

General Reaction of Non-metals with Water:

e.g. SO3 + H2O :

(sulfuric acid)

non-metal oxides => covalent bonds

O-H bonds are weak
 NM=O bonds pull electron density away from O-H, polarising these bonds, thereby
making them easier to break

e.g. H2SO4 → SO42- + 2H+

sulfuric acid sulfate

 Breakage of O-H bonds may also produce more stable compounds, due to resonance:

e.g. Sulfate:

Pauling’s rules

(1.) For general oxyacid OpE(OH)q, pKa ≈ 8 - 5p + 5

(2.) For polyprotic acids (i.e. q>1) each successive pKa increases by ~5 units

Where E is any non-metal, p = # E=O bonds, q = # O-H groups

e.g. (1.)

Why this formula works:

More E=O bonds means:
 more electrons pulled from OH groups, making OH bonds weaker, in turn making it a
stronger acid
 more resonance contributors to stabalise conjugate base

e.g. (2.)

2 S=O bonds, so p=2

∴ pKa1 ≈ 8-5(2) = -2
next pKa increases by 5 units so

pKa2 ≈ -2 + 5 = 3

Remember: the lower the pKa value, the stronger the acid

E.g. predict which of the two acids in each pair is stronger

A: B:
a)

vs.

b)

vs.

c)

vs.

Solution:
a)
A: B:

p=2 p=1
∴ pKa ≈ 8-5(2) ∴ pKa ≈ 8-5(1)
= -2 =3

∴ A is more acidic

b)
A: B:

p = 2, second pKa no protons, ∴ can’t act as an acid

∴ pKa ≈ 8 – 5(2) + 5
=3
∴ A is more acidic
c)
A: B:
p=1 p=0
∴ pKa ≈ 8 – 5(1) ∴ pKa ≈ 8 – 5(0)
=3 =8

∴ A is the stronger acid

Metalloid Oxides
- Tend to be neither strongly acidic nor strongly basic
- Most don’t react with water
(some metal oxides with metalloid tendencies don’t react with water either)

- Will often react with both acids and bases

 are amphoteric oxides

aq. acid
[Al(OH2)6]3+ neutralising an acid (acting as a weak base)
e.g. Al2O3
aq. base
[Al(OH)4]- neutralising a base (acting as a weak acid)

Quirky Boiling Points

There is a particulary pronounced change in lots of properties between 2 nd and 3rd periods

Compound B.P. (° C) Compound B.P. (° C) Compound B.P. (° C)

NH3 -33 H2O 100 HI 20
PH3 -87 H2S -65 HCl -85
AsH3 -60 H2Se -45 HBr -69
SbH3 -25 H2Te -15 HI -35

Elements N, O, F don’t follow trends.

This is often discussed as being due to H-bonding, i.e electronegativity

But why are these atoms so electronegative?

 Because they have high Zeff
Small size -> high charge-to-size ratio

The Uniqueness Principle

A periodic trend where the second period elements are significantly different than other
elements in their respective groups
- π -bond formation

Bond Typical bond energy Bond Typical bond energy

(KJ mol-1) (KJ mol-1)
C-O 340 Si-O 370
C=O 800 most favourable Si=O 640
2xC-O 680 2xSi-O 740 most favourable

Hence CO2 is a discrete molecule,

O=C=O

while SiO2 is a diamandoid polymer (containing only Si-O bonds)

p orbitals are p orbitals are

- close - further away
- similar in size - silicon p orbital is much larger
- similar in energy level - different in energy level

π -bond favoured π -bond less favourable

Carbon Nitrogen Oxygen
Cn N≡N O=O
- several allotropes - π -bonded - π -bonded
- all but one contain π -bonds

Silicon Phosphorus Sulfur

Sin P4/Pn S8
(no π -bonds)

(no π -bonds) and other cyclic structures

(no π -bonds)

Uniqueness Principle Summary

- 2nd period elements much smaller than 3rd period elements

 high electronegativity → H-bonding
 higher ionisation energies
 readily form π -bonds

These properties make organic chemistry unique

Another quirk – the diagonals

We already know there are similarities in properties within groups and periods

Additionally, there are sometimes striking similarities in elements that are diagonal to each
other

 particularly for: Li/Mg, Be/Al, B/Si

e.g. can form alkyl lithiums and alkyl magnesiums easily but not alkyl sodiums or alkyl
berylliums

Why?
Trends that increase going right and decrease going down can cancel out to give roughly the
same ionisation energy, atomic radius etc., which leads to similar properties
Transition Metal Chemistry

- quite different to main group elements

- include most elements a non-chemist would think of as metal (iron, nickel, copper, silver
etc.)

- form complexes
 often paramagnetic or magnetic

 paramagnetic compounds are very hard to study under NMR

 complexes are often colourful

Periodic Trends of Transition Metals

Don’t really follow the same trends as other elements.
However, they stay within a pretty narrow range of similar values (for ionisation energy, atomic
radius etc.)

Ionisation Energies of Transition Metals

- relatively low ionisation energies
 relatively easily oxidised

Oxidation States of Transition Metals

- complicated
- Reminder: when adding electrons, we follow the Aufbau principle

3d is lower than 4s

However, when removing electrons, 4s gets lost first

e.g.

Ni: [Ar]3d84s2

Ni+: [Ar]3d84s1

Ni2+: [Ar]3d8

Ni3+: [ Ar]3d7

Sometimes 4s are only half filled before 3d

 e.g. Cr: [Ar]3d54s1 Ag: [Kr]4d105s1
10 1
Cu: [Ar]3d 4s

Ru, Rh, Pd, Ah, Pt, Au, Mo all have only one e- in s orbital

Trends:

Element Maximum Oxidiation State Explanation

Sc +3 Sc: [Ar]3d14s2
Only has 3 outer electrons to
lose
Ti +4 Has 4 outer electrons to lose
V +5 ⋮
Cr +6
Mn +7
Fe +6 Fe onwards, too hard to
remove enough electrons to
achieve noble gas electron
arrangement

Sc and Zn only have 1 possible oxidation state

 3d subshell stays filled:
Zn: [Ar]3d104s2
Zn2+: [Ar]3d10

+2 oxidation states are common as most transition metals have 2 4s electrons which can be
easily removed
General rule for filling subshells:
- Aufbau for elements 1-18 (H – Ar)
- K: [Ar]4s1 4s before 3d after Argon
2
Ca: [Ar]4s
Sc: [Ar]3d14s2 Once transition metals start, 3d is filled, leaving 2 outer 4s
2 2
Ti: [Ar]3d 4s electrons (this is why transition metals have similar valences of
3 2
V: [Ar]3d 4s +2)
* Cr: [Ar]3d54s1
Mn: [Ar]3d54s2
Fe: [Ar]3d64s2exceptions: only one electron in 4s
Co: [Ar]3d74s2
Ni: [Ar]3d84s2
* Cu: [Ar]3d104s1
Zn: [Ar]3d104s2

Cu is the 4th period transition metal that can have an oxidation state of +1. This is because it
only has one electron in its outer 4s orbital

Coordination Complexes

CoCl3 is a compound, originally thought to be composed of Co3+ and 3xCl-

But it was found that CoCl3 reacts with NH3 to form several different compounds, all of which
are different colours

CoCl3(NH3)6 CoCl3(NH3)5 CoCl3(NH3)4 CoCl3(NH3)4

The structure of these, and reasons for different colour was unknown, so they were just
referred to as ‘complexes’

Alfred Werner
Identified the correct structure of transition metal complexes

How the structure was identified:

- “free” Cl- ions were tested for by adding Ag+ and measuring how much AgCl was formed

CoCl3(NH3)6 CoCl3(NH3)5 CoCl3(NH3)4 CoCl3(NH3)4

↓ ↓ ↓ ↓
3 free Cl- 2 free Cl- 1 free Cl- 1 free Cl-

Sophus Mads Jørgensen

Came up with “chain theory”
 said that structure had ammonium chains bound to the Co, and Cl atoms bound to the
Co were not free, while Cl atoms at the end of ammonium chains were free

CoCl3(NH3)6 CoCl3(NH3)5 CoCl3(NH3)4 CoCl3(NH3)4

↓ ↓ ↓
NH3Cl Cl Cl
/ / /
Co – NH3Cl Co – NH3Cl Co – Cl
\ \ \
NH3NH3NH3NH3Cl NH3NH3NH3NH3Cl NH3NH3NH3NH3Cl

- based on incorrect logic that if cobalt was in the 3+ oxidation state, it could only form 3
bonds

Werner:
Said there were 2 influencing factors:

- Hauptvalenz: primary/ionisable valence (oxidation state)

- Nebenvalenz: secondary/non-ionisable valence (coordination number)

i.e. how many things are bound

Said that number of things bound is not necessarily the same as oxidation state

Actual structure of CoCl3(NH3)6 : Nomenclature:

[Co(NH3)6]Cl3
Cl- ions exist separate from the structure

Actual structure of CoCl3(NH3)5

[CoCl(NH3)5]Cl2

Cl’s not bound go on the outside of the

square brackets

Oxidation State: formal charge on the metal ion (difference between number of protons and
electrons)

Coordination Number: the number of bonds the metal ion forms

Working out oxidation state and coordination number

Coordination number:
just count the number of substituents (ligands) on the metal

Oxidation state:
look at the atoms of the substituents (ligands) from the metal. Excluding the
coordination bond (the bond to the metal) determine whether the elements form more
or less (or the same) as usual.
For n less bonds than normal, ligand has n- charge
For n more bonds than normal, ligand has n+ charge

E.g. Determine the coordination number and oxidation state of the metal in the following
complex:

Solution:

4 substituents so coordination number = 4

NH3 has usual number of bonds

N=C=S has usual number of bonds for S and C but one less for N

∴ N=C=S ligand has a charge of 1-

There are two N=C=S ligands, and the overall molecule is neutral

∴ Pt has oxidation state of 2+

“Normal” bond numbers:

C:4
N:3
O:2 C=O is neutral
S:2
Halides : 1

Things outside the brackets:

Behaves just like an ionic salt
 solid: ionic attraction
 aqueous: free to move around in solution
Coordinate bonds remain intact in all solvents

Linus Pauling
- came up with Pauling’s rules
- came up with:
“Postulate of the essential electroneutrality of atoms”
 a.k.a Pauling’s Electroneutrality Principle

1948: “the electronic structure of substances is such as to cause each atom to have essentially
1
zero resultant electrical charge, the amount of leeway being not greater than about ± ,
2
and these resultant charges are possessed mainly by the most electropositive and
electronegative atoms and are distributed in such a way to correspond to electrostatic
stability”

1970: “stable molecules and crystals have electronic structures such that the electric charge of
each atom is close to zero (between -1 and +1)”

This explains why ions form coordinate covalent bonds

e.g.s
H3N: H+ NH4+

H3N: Co3+ [Co(NH3)]3+

Coordination bonds can be thought of as a mix of ionic and covalent bonding

Ionic Bond Coordination Bond Covalent Bond

Dissociates in polar No significant dissociation, Does not dissociate
solvents can be reversed
Large electronegativity Moderate Zero or small
difference electronegativity electronegativity
difference difference

<- proper way to draw, charge is spread

across whole molecule

Octahedral complex
has shape: forms an 8-faced shape,
hence “oct-“

This shape occurs as it is the furthest away six substituents can point

More than 6 substituents is unfavourable as it puts substituents too close together

Large metals such as plutonium can form more than 6 substituents (Pu has 9)

Less than 4 substituents is rare since it is not enough donors to spread positive charge. Can be
achieved by small metals with low charges.

4-Coordinate Geometries

Tetrahedral

or Square planar
- more strained
- requires small ligands

5-Coordinate Geometries

6x90° angles Trigonal bipyramidal

3x120° angles

8x90° angles Square pyramidal

6-Coordinate Geometry

all angles 90° Octahedral

Coordination number is a balance between maximising the number of metal-ligand (M-L)
bonds, while minimsing steric clashes
- Larger oxidation states and/or large metals generally favour higher coordination number

- Ligands will generally be as far away as possible (tetrahedral, trigonal bipyramidal,

octahedral) but sometimes electronic factors can over-ride this (square planar, square
pyramidal)

Ligands
- can be ions or molecules
- neutral or negatively-charged

- are Lewis bases

-> electron pair donors

monodentate/unidentate
only bind to one atom

- things that can bind strongly to H+ (strong bases) will bind strongly to transition metals
(be good ligands)

bidentate ligands
molecule with two groups that can donate electron pairs to a metal

e.g.

Chelate
ligand where two or more donors bind to the same metal

e.g.
Chelating Ligand Non-chalating Ligands

* bind more strongly

Tridentate, tetradentate, pentadentate, hexadentate...

polydentate

Bridging Ligands
Ligands with two or more electron donating groups that can bind to multiple metals (forming a
bridge between 2 or more metals)

- some ligands with multiple electron donating groups can only form bridges, and not act
as chelating ligands, as the shape of the ligand may make polydentate bonding
unfavourable

Nuclearity
number of metals joined together in a complex by a briding ligand

- dinuclear complex: 2 metals

- trinuclear complex: 3 metals
⋮

Bridging ligands can stick metal complexes together into polymers called coordination polymers
 these can be 1D, 2D or 3D

Some ligands can bridge or form single bonds:

−¿¿
e.g. Cyanide: C≡N

Singly-bonding or bridging
−¿¿ −¿¿
Ln M −C ≡ N Ln M −C ≡ N −ML❑n
−¿N =C =S¿
e.g. Thiocyanate: N ≡C−S−¿ ↔ ¿

singly-bonding or bridging
(2 ways)
−¿¿ −¿¿
Ln M −N=C=S Ln M −N ≡ C−S−ML n

−¿ ¿
Ln M −N ≡ C−S

Isomerism in Coordination Complexes

Isomers
 (same formula)

Structural Isomers Stereoisomers

(different bonds) (same bonds, different arrangements)

Coordination- Linkage Geometric Optical

Sphere Isomers Isomers Isomers Isomers

Coordination-Sphere Isomers
differ in which substituents form coordination with a metal and which are “free”

e.g. molecular formula Co(Br)(NH3)5(SO4) has coorination formulae:

[Co(NH3)5(SO4)]Br or [Co(Br)(NH3)5]SO4
O O +
S 2+
O O

SO42-
−¿¿
Br

Linkage Isomers
differences in the way ligands bind to the metal
- occurs when ligands have more than one electron pair donors
e.g. thiocyanate can form linkage isomers, such as:
C S
S−C ≡ N
S−C ≡ N
C and
S
cis-[Pd(NCS)2(NH3)2] cis-[Pd(SCN)2(NH3)2]
Stereoisomers

Square Planar

geometric isomers
- different chemical/physical properties

Tetrahedral

optical isomers
- same chemical/physical properties
excluding rotation of polarised light and
biological properties (e.g. taste)

mirrors of each other

Stereoisomers for Bidentate Ligands
The bidentate ligands can not swap around (they must be adjacent)
Isomers can still form depending on arrangement of other substituents
 hence possible for tetrahedrals:

also depends on symmetry of the bidentate ligand

i.e. if A=B, not isomers

e.g.

cisplatin transplatin
anti-cancer activity no anti-cancer activity (and toxic)

5-Coordinate Complexes (trigonal bipyramidal/square pyramidal)

5-coordinate complexes tend to not form isolable isomers (isomers can not be isolated)
This is because there is a very low energy gap between trigonal bipyrmaidal and square
pyramidal, allowing such complexes to switch between isomers
6-Coordinate Complexes
Lots of isomers

[MA5B] – no isomers

=> This is what allows for differences in colour, as

seen earlier with [Co(Cl)2(NH3)4]Cl :
trans-[MA4B2] cis-[MA4B2]

Geometric isomers
↓↓
green purple
[MA3B3]:

also geometric isomers

mer-[MA3B3] fac-[MA3B3]

A’s and B’s extend A’s and B’s extend in different directions to form two opposite
in the same plane triangular faces
mer = meridional fac = facial
-> forms a line -> each groups of 3 donors cover one face of the metal
en = A−A mirror plane

trans-[M(B)2(en)2] cis-[M(B)2(en)2 cis-[M(B)2(en)2

geometric isomers
optical isomers

Nomenclature for Octahedral Complexes

Δ = right-handed helix
(delta)

Λ = left-handed helix
(lambda)
l for ‘left’

This is best seen when the non-bidentate (B) ligands are in the flat plane

Λ -cis-[M(B)2(en)2] Δ -cis-[M(B)2(en)2]

Λ -cis-[M(en)3] Δ -cis-[M(en)3]
E.g.
Do the following compounds have stereoisomers? If so, how many, and are they optical and/or
geometric?

a) [Fe(ox)3]3- b) [Fe(bpy)2(Cl)2 c) [Fe(Cl)3(tpy)]

Solution:

a) 2 optical isomers)

b) 3 isomers (geometric and optical)

c) no isomers
tpy can only form mer-, too big to form fac-

Naming Inorganic Compounds

Writing Formulae:
- coordinated things go in square brackets
- metal comes first
- ligands in alphabetical order (element symbol, not name)

[M(A)x(B)y(C)z...]

- cations go before Cn+[...]n-

- anions go after [...]n+An-
 Writing Names:

Inside brackets:
- Ligands before metal, in alphabetical order
- Metal at end with oxidation state in brackets (in Roman numerals) all one word

quirks:
* negatively charged ligands get re-named
-> last e become o
e.g. chloride -> chlorido
hydroxide -> hydroxido
acetate -> acetato
cyanide -> cyanido
⋮ etc.

* really common ligands have special names:

water -> aqua
ammonia -> ammine (not to be confused with amine)
carbon monoxide -> carbonyl

* 2 different ways to indicate how many ligands:

-> simple ligands (monodentate, don’t already contain di, tri, tetra...) => di, tri, tetra,
penta, hexa, ...
-> complex ligand (polydentate, already contain di, tri, tetra...) => bis, tris, tetrakis,
pentakis, hexakis,... and these prefixes come outside brackets

e.g. dichloro, tetrapyridine, bis(ethylenediamine), bis(bipyridine)

 These prefixes are not considered during alphabetical ordering

Examples:

H2 N NH2 ligands are neutral

Cl ligands have -1 charge

∴ Co has oxidation state of +2

∴ Ending will be cobalt (II)

chlorine , ethylenediamine
↓ -1 ↓x2, and complex
chlorino tris(ethylenediamine)
↓ x2
dichlorino
bidentate ligands on left when monodentate ligands are in same plane
∴ left-handed helix
∴Λ
bidentate ligands are adjacent,
∴ cis

∴ name is Λ -cis-dichloridobis(ethylenediamine)cobalt(II)

ammine ligands have neutral charge

∴ cobalt has oxidation state of +3

6 ammine ligands
↓
hexaammine

no isomers

∴ name is hexaamminecobalt(III)

iodine ligand has -1 charge

aqua ligands have neutral charge
∴ copper has oxidation state of +2

aqua , iodide
↓ x4 ↓ -1 and x1
tetraaqua iodido

5-coordinate geometry, so no isolable isomers

∴ name is tetraaquaiodidocopper(II)

E.g. Draw mer-triamminetribromidocobalt(III)

Each of the two ligand types must be in the same plane (mer)

Each Br has -1 charge while Co has +3 charge, ∴ overall compound is neutral

Stuff Outside Brackets

If complex has positive charge, anion goes after with a space between the complex and the
anion(s).
Number of anions is not given, as it can be worked out from the oxidation state

e.g.

hexaamminecobalt(III) chloride

If complex has negative charge, cation goes before with a space between the cation(s) and the
complex.
Number of cations is not given.
Complex gets “ate” added after the metal. If the meta had “um” or “ium”, these are removed
e.g. cobaltate, zincate, nickelate, titanate, chromate
Quirks:
Iron -> ferrate
Copper -> cuprate
Manganese -> manganate

e.g.

sodium tetrachloridocuprate(II)

d-orbital electrons

Cobalt3+ and iron2+ have [Ar]d6 electron configuration yet are often diamagnetic
-> implies no unpaired
electron

[Ar]d6 however has outer d-orbital:

__ __ __ __ __
Valence Bond Theory does not work well for coordination complexes
↓
Instead, we use:
Crystal Field Theory
- assumes purely ionic interaction between M and L
 in reality, not true, but still allows for a simple model which accounts for most
complexes
 ligand field theory is a more complex model

- focuses on the lone electron pair on the L and the valence electrons (3d electrons) of
the M

- assumes a ligand is just a pair of electrons located in a precise spot in space

Since electrons repel, there will be an unfavourable interaction between metal d-orbital and
the ligands

d-orbitals:

2D Diagrams
dxy, dxz and dyz orbitals point between ligands, so experience little repulsion. We call these t2g
orbitals

d x − y and d z orbitals have regions that point at ligands, so experience significant repulsion.
2 2 2

(Both have the same amount of repulsion.) We call these eg orbitals

Δo
- related to how much the ligands and d orbitals repel each other

- more basic ligand → electron pairs more “accessible” → greater repulsion with d-
orbitals
↓
higher Δ o

 The more basic the ligand, the greater the value of Δ o

e.g. Cl−¿¿ is a weak field ligand

-> not good at sharing electrons, low Δ o
-> have small crystal field splitting

e.g. NH3 is a strong field ligand

-> good at sharing electrons, high Δ o
-> large crystal field splitting
3d1
3d2
3d3
3d4 : either t2g or eg : there is an energy cost associated with putting electrons in the higher eg
orbital (governed by Δ o) and there is an energy cost associated with pairing electrons
 high Δ o →t 2 g ,low Δ o →e g

eg eg
__ __ 1 __ __ 1 1 1 1
t2g spin = 4 × =2 t2g spin = + + − =1
2 2 2 2 2
__ __ __ ∴ called high spin __ __ __ ∴ called low spin
Δ o < p (pairing energy) Δo > p

5
d
High spin: Low spin:
__ __ eg __ __ eg

__ __ __ t2g __ __ __ t2g

5 1
s= s=
2 2

6
d
High spin: Low spin:
__ __ eg __ __ eg

__ __ __ t2g __ __ __ t2g

s=2 s=o
 No unpaired electrons so diamagnetic
7
d
High spin: Low spin:
__ __ eg __ __ eg

__ __ __ t2g __ __ __ t2g

3 1
s= s=
2 2

8
d
Only one arrangement:
__ __ eg

__ __ __ t2g

9
d
Only one arrangement:
__ __ eg

__ __ __ t2g

d 10
Only one arrangement:
__ __ eg

__ __ __ t2g

d8, d9 and d10 are easy to use NMR on

d orbitals in tetrahedrals
Ligands are now on the corners of a cube
(diagram)

Now ligands are closer to dz2 and dx2-y2 orbitals are further
dzx, dyz and dxy, so higher from ligands so lower in energy
in energy