Introductory Chemistry B CH4751 Lecture Notes 11-20: Dr. Erzeng Xue

CH4751 Lecture Notes 11-20 (Erzeng Xue)
Introductory Chemistry B CH4751

Lecture Notes 11-20
Dr. Erzeng Xue
CH4751 Lecture Notes 11 (Erzeng Xue)
Chemical Reactions
Chemical Reaction - Observation

Reaction (1)
CH4 + 2O2 CO2 + 2H2O
Reaction (2)
CH4 + CO2 2CO + 2H2
When carrying out these reactions we found that
at 400K (123C), the reaction (1) will proceed and reaction (2) will not
at 1000K(723C), reactions (1) & (2) both proceed; but
rxn (1) can go complete (until CH4 or CO2 consumed completely)
rxn (2) wont complete (with a feed CH4=CO2=1 & CO=H2=0, max. conv.=63% at 1000K)
The reaction (1) will give out heat, but the reaction (2) will require heat.
Why?
Chemical Reactions
Chemical Reaction Thermodynamics
Each molecule contains certain types and quantity of chemical energy
There is always energy change In a chemical reaction because of
breaking / reformation of chemical bonds

out-giving or in-taking heat
There are different energies associated with a substances & a reaction

(A systematic study of various forms of energy & their changes is called
Thermodynamics)
We will learn some of these energies
The meanings
How to get values / do simple calculate
How to use them as a tool to study chemical reactions

3
Chemical Reactions
The heat of formation, H, (also called Enthalpy of Formation or Enthalpy)
H is an energy associated with heat

H is specific for each substance and is dependent of temperature & pressure
e.g. at 1000K: HCH4=-89, HO2=0, HCO2=-394, HH2O=-241, HCO=-111, HH2=0
(kJ/mol)
(H values for various substances can be found in physical chemistry/Chem Eng handbooks)
In a reaction we are interested in the enthalpy change, DH, which is calculated using
DHT0 ( vi Hi0,T )prod ( vi Hi0,T )reac
refers to standard pressure (1 atm.)

Temperature
For
Rxn(1) CH4 + 2O2 CO2 + 2H2O
DH1000=-801 kJ/mol
Rxn (2) CH4 + CO2 2CO + 2H2
DH1000=+260k J/mol
The meaning
When DH<0, a reaction releases heat reaction is exothermic, as in rxn (1)
When DH>0, a reaction requires heat reaction is endothermic, as in rxn (2)

4
Chemical Reactions
The Gibbs Free Energy, G, (also called Free Energy)

G
is a thermodynamic function related to a reaction. It is a function of H, T & S (entropy)
is specific for each substance & is a function of H, T & S (entropy)
e.g. at 1000K: GCH4=-+30, GO2=0, GCO2=-395, GH2O=-192, GCO=-200, GH2=0

(kJ/mol)
(G values for various substances can be found in physical chemistry/Chem Eng handbooks)
The Gibbs Free energy change, DG, in a reaction can be calculated using
DGT0 ( viGi0,T )prod ( viGi0,T )reac

For
Rxn(1) CH4 + 2O2 CO2 + 2H2O
DG400 DG1000=-801 kJ/mol
Rxn (2) CH4 + CO2 2CO + 2H2
DG400=+145, DG1000=-24 kJ/mol
Use of DG - Rxn(1) DG <0 at 400 & 1000K-spontaneous, Rxn(2) DG <0 at 400K, will not proceed
for a reaction at
constant T, P,
DGT 0 reaction can proceed (but we dont know how fast it will be!)
DGT 0 reaction at equilibrium (no further change possible-dead state)

DG 0 reaction will NOT proceed (or can proceed backward!)
T
5
Chemical Reactions

Example of DHT calculation
CH4(g) + 2O2(g) CO2(g) + 2H2O(g)
Coeff.
H400(
H1000
1
-77
-89
2
0
0
1
-393
-394
2
-242
-248
CH4 + CO2 2CO + 2H2

1
-77
-89
1
-393
-394
2
-110
-111
2
0
0
kJ/mol
kJ/mol
Equation to use
DH400 =[1x(-393)+2x(-242)]-[1x(-77)+2x(0)]= -800 kJ/mol

DH1000 =[1x(-394)+2x(-248)]-[1x(-89)+2x(0)]= -801 kJ/mol
Reaction (1)
Reaction (2)
DH400 =[2x(-110)+2x(0)]-[1x(-77)+1x(-393)]=+250 kJ/mol
DH1000=[2x(-111)+2x(0)]-[1x(-89)+1x(-393)]= +260 kJ/mol
Note: The heat of formation of single element gases (O2, H2, N2 etc) is defined as zero.
6
Chemical Reactions

Example of DHT calculation
CH4(g) + 2O2(g) CO2(g) + 2H2O(g)
Coeff.
1
2
1
2
CH4 + CO2 2CO + 2H2

1
1
2
2
G400(
-42
-394
-224
-42
-394
-146
kJ/mol
G1000 +19
-396
-193
+19
-396
-200
kJ/mol
Equation to use
DG400 =[1x(-394)+2x(-224)]-[1x(-42)+2x(0)]= -800 kJ/mol

DG1000 =[1x(-396)+2x(-193)]-[1x(+19)+2x(0)]= -801 kJ/mol
Reaction (1)
Reaction (2)
DG400 =[2x(-146)+2x(0)]-[1x(-42)+1x(-394)]=+144 kJ/mol

DG1000=[2x(-200)+2x(0)]-[1x(19)+1x(-396)]= -23 kJ/mol
Note: The Gibbs Free Energy of single element gas (O2, H2, N2 etc) is defined as zero.
7
Chemical Reactions
The values of DGT and DH T

Equations
In both cases G and H values for the reactants and products have to be those at the
reaction temperature, indicated by the subscript.
For common substances, G and H values are given as a function of T in handbooks - okay
For some less common substances, you may only find values at 298K, G298 and H298
How do you convert values of G298 and H298 to those of GT and HT ?
Here is the equations you can use to calculate the values of GT and HT from G298 and H298
0
i ,T
0
i ,298
DC p ,i dT DH phase change,i
T
298
Gi0,T H i0,T - T Si0,T
0
where Si0,T S298
DC p ,i
298
dT Qphase
T
Tj
in which, ST is the entropy and Cp is the heat capacity at constant pressure

8
Chemical Reactions
Summary
Will a reaction proceed in the direction specified?

Check DGT value of the reaction. The DGT value of a reaction can be calculated by

The G values of reactants / products can be found in literature. Remember
for a reaction at
constant T, P,
DGT 0 reaction can proceed (but we dont know how fast it will be!)
DGT 0 reaction at equilibrium (no further change possible-dead state)

DG 0 reaction will NOT proceed (or can proceed backward!)
T
Is a reaction exothermic or endothermic?

Check DHT value of the reaction. The DHT value of a reaction can be calculated by

The H values of reactants / products can be found in literature
9
Chemical Reactions
Chemical Reaction Equilibrium
Until now we assume reaction A + B C + D goes to complete
Meaning a reaction only stops when either A or B is consumed completely
Experimental observations
Some reactions will cease without complete consumption of limiting reactant
Without altering reaction conditions (T, P, [ ] etc.) the ratio of conc. remains constant
After a change (T, P, [ ] etc.), the ratio of concs changes to another constant value
Example 1: NH3(aq) + H2O(l) D NH4+(l) + OH-(aq)

Follow concentrations of each component with time at constant T and P,
[NH4]2
[NH4 ][OH ]
at t
constant
[NH3 ][H2O]
[NH4]1
After changing T, a new constant ratio is established

If [NH3] is reduced the amount [NH4] decrease accordingly
while the ratio above remains constant
[NH3]1
[NH3]2
We say the reaction has reached equilibrium state

10
Chemical Reactions
Experimental observations
Example 2: 2NO(g) + O2(g) D 2NO2(g)
Again at constant T and P, when t
2
PNO
2
2
NO O2
P P
constant
NO2
NO
O2
Reaction equilibrium is achieved when t
We say the reaction has reached equilibrium state
The ratio of product concentration to reactants, with the stoichiometry coefficient as the
power index, is called reaction quotient
When reaction quotient = constant value reaction reaches equilibrium
The value of reaction quotient at equilibrium, is called equilibrium constant, Keq
At equilibrium, reactants may or may not be consumed completely

e.g. A feed gas mixture: NO=500ppm, O2=10%, N2=89.95%, achieves equilibria at the following Ts
Temperature
/ C
NO remaining at equil
/ ppm
NO conversion at equil
/%
50
325
500
96.5
390
100
80.3
22
11
Chemical Reactions
Important concepts of reaction equilibrium
2NO(g) + O2(g) D
2NO2(g)
Is the reaction between reactants still going on?

YES.
Reaction goes forward as well as reverses.
At equilibrium:
Rforward = Rreverse
though there is no NET change of all conc.s
The equilibrium constant, Keq, has a meaning of
Keq=Rforward / Rreverse
2
PNO
2
Kp
2
PNO
PO2
NO2
NO
O2
t
Changing T causes both Rforward & Rreverse to change, leading to a new Keq.
If Keq >>1, which means Rforward >> Rreverse, the reaction tends to go forward
If Keq <<1, which means Rforward << Rreverse, the reaction tends to go backward
Will there be an equilibrium constant for reactions that go complete?

YES.
fixed.
There is Keq for all reactions (at a constant P) once T and concs are
For a reaction that tends to go complete, Rforward >> Rreverse (Keq >>1).
12
Chemical Reactions
Equilibrium constant and Gibbs Free Energy

For reaction
vAA + vBB D vCC + vDD
Remember: The value of DG determines the direction of reaction

for a reaction at
constant T, P,
DGT 0 reaction is spontaneous
DGT 0 reaction at equilibrium (no further change possible)

DG 0 reverse reaction is spontaneous
T
No more change possible reaction in equilibrium DG= 0
Is the DG value related to the equilibrium constant?

YES. DG and Keq are related by the equation below (calculate one from the other)
DGT= - RTln(Keq)
13
Chemical Reactions
Equilibrium constant - for different type of rxns

General form:
vAA + vBB D vCC + vDD
for liquid phase rxn

for gas phase rxn
[C]vC [D]vD PCvC PDvD

K eq
f (T )
[A]v A [ B]vB PAv A PBvB
2
PNO
2
gas phase
2NO(g) + O2(g) D 2NO2(g)
Kp
gas-solid phase
CaCO3(s) D CaO (s)+CO2(g)
K p PCO2
liquid phase
NH3(aq)+H2O(l) D NH4
[NH4 ][OH ]
Kc
[NH3 ][H2O]
liquid-solid
Cu(OH)2(s) D Cu2+(aq)+2OH- (aq)
K c [Cu 2 ][OH ]2
gas-liquid
NH3(g)+H2O(l) D NH4OH(aq)
K p 1 / PNH 3
+(l)+OH-(aq)
2
PNO
PO2
For reactions that have gas components, we normally use pressure to represent the concs
For reactions involves gas+liquid or gas+solid, only gas terms appear in the Keq expression
14
Chemical Reactions
Factors Affecting Reaction Equilibrium
Le Chateliers Principle
When a system in equilibrium is subjected to an external stress, the system will
establish a new equilibrium, when possible, so as to minimise the external stress
Stresses: Changes in [ ], temperature or pressure
Example:
N2(g) + 3H2(g) D 2NH3(g) + heat
(exothermic)
a) Effect of ([ ]). Increasing [ ] of substance shifts equil. in the direction of the long arrow
N2 + 3H2
2NH3 + heat
N2 + 3H2
2NH3 + heat
N2 + 3H2
2NH3 + heat
Kp
2
PNH
3
PN 2 PH32
PN 2 or PH 2 PNH3
const
PNH3 PN 2 & PH 2
b) Effect of heat. Addition or removal of heat at constant temperature

Addition of heat: N2 + 3H2
2NH3 + heat
c) Effect of Pressure. (only affects reactions that have volume change before & after).
Increase in pressure:
N2 + 3H2
4 volumes
2NH3 + heat
2 volumes
15
Chemical Reactions
Write the equilibrium expression for the following reactions and

determine the units for Keq:
PO32
1) 2O3(g) D 3O2(g)
[atm]3
Kp 2 ,
[][atm]
2
PO3 [atm]
2) Ag+(aq) + 2NH3(aq) D Ag(NH3)2+(aq)
[Ag(NH3 ) 2 ]
[mol/l]
Kc
,
[
]
[] [mol2 /l2 ]
2
2 2
[Ag ][NH3 ]
[mol/l][mol /l ]
3) 2NaN3(s) D 3Na(s) + 3N2(g)
K p PN32 , [][atm3 ]
4) 2Na(s) + Cl2(g) D 2NaCl(s)
Kp
5) 2NaCl(s) D 2Na(s) + Cl2(g)

6) N2(g) + 3H2(g) D 2NH3(g)
1
, [][1/atm]
PCl 2
K p PCl 2 , [ ][atm]
2
PNH
3
[atm2 ]
Kp
, [ ]
[][1/atm2 ]
3
3
PN 2 PH 2
[atm][atm ]
Note 1. The Keq expression depends on how the rxn equation is written (compare rxns 4&5).
2). The unit of Keq depends on the way how the rxn eqn is written & the unit used of each.
16
Chemical Reactions

1. Analysis shows that a mixture of N2 (2.46 atm), H2 (7.38 atm) and NH3 (0.116 atm) at
472C in reaction (N2(g) + 3H2(g) D 2NH3(g)) is in equilibrium state.
Calculate: 1) Keq; 2) DG; 3). The total pressure. 4) Will the rxn be push to the product by
decreasing the reaction pressure? Give reason why? 5) Will the removal of NH3 from
reaction mixture promote the product formation? Explain why.
2
PNH
3
(0.166) 2
2.79 105 /atm2

3
(2.46)(7.38)
1)
Kp
2)
DGT= - RTln(Keq)=-8.314x(472+273)ln(2.79x10-5)=65 kJ/mol
3)
Ptotal= PN2+PH2+ PNH3=2.46+7.38+0.116=9.956 atm
PN 2 PH32
4) A decrease reaction P favours the reverse rxn because Volreactant > Volproduct.
5) Yes. As Keq=P2NH3/(PN2xP3H2)=constant, the removal of NH3 will reduce PNH3, to
compensate the change, more N2 and H2 will be converted to NH3 in order to keep
the same Keq (reaction quotient).
17
Chemical Reactions
Chemical Reaction
What we know about a chemical reaction so far
Reaction equation - quantitative representation of a chemical reaction
We can judge if a give chemical reaction would proceed in the direction specified
If DH < 0, reaction is exothermic; if DH > 0, reaction is endothermic
For reactions that are feasible, to what extent they will complete
A reaction has a tendency if DG of a reaction is smaller than zero
We can decide if a given reaction gives out or takes up heat
Reaction stoichiometry coefficients and balancing reaction equations
Chemical reaction equilibrium, equilibrium constant
Now we know a rxn would proceed in the direction specified, questions are:
- how fast that reaction is going to proceed under give conditions?
- how to quantitatively describe the rate of a reaction and make comparison?

- how can we explain that some reactions occur faster than others?
e.g. 2NO(g) + O2(g) = 2NO2(g) (slow); 2NaN3 = 2Na + 3N2 (very fast)
18
Chemical Reactions
Chemical Reaction Kinetics
Chemical reaction kinetics study the rate of chemical reactions
Definition of chemical reaction rate
The number of moles of a reactant converted (consumed) in a reaction per unit time
for a reaction
rA
A+BC+D
[A]2 [A]1
t 2 t1
or rA
d [A]
dt
(mol/s)
When we say rate we always refer to ONE of the components in the reaction
The minus sign refers to that the concentration of reactant decreases in reaction
Reaction rate equation (or kinetic equation)
Arrhenius equation
Many forms exist

d [A]
-E
The most common one rA
k[A]a [B] b [C] l [D] d in which k A0 exp a
dt
where
A0
Ea
a,b,l,d
R
T
RT
reaction rate constant
pre-exponential factor
reaction activation energy
reaction orders with respect to A, B, C, D, respectively
gas constant
reaction temperature in Kelvin scale
Kinetic
parameters
19
Chemical Reactions
Meanings of kinetic parameters, k, A0, Ea, a,b,l,d
-E
k A0 exp a
RT
Reaction rate constant, k
It tells how fast a reaction can occur

It is a constant dependent on temperature but independent of concentrations
Pre-exponential factor, A0
It refers to the frequency of collision between molecules, the higher frequency, the faster rxn
Reaction activation energy, Ea
It can be understood as the energy

barrier for a reaction to overcome
The higher Ea value is, the more

difficult for a reaction to occur
energy
Reaction orders w.r.t. each component, a,b,l,d
Ea
reactant
product
reaction process
The magnitude of these values reflects the effectiveness of each component in the reaction
The values of a,b,l,d can be positive or negative or zero
The values of a,b,l,d can be integrals or fraction
All these kinetic parameters have to be determined experimentally

20
Chemical Reactions
Factors affecting the rate of a chemical reaction

-E
rA A0 exp a [A]a [B] b [C] l [D] d
RT
Reaction temperature, T
An increase T will lead to increasing k, thus reaction rate.

The dependence of k on T is given by differentiating k expression,
-E
E
dln k
-E
k A0 exp a ln k ln A0 a
a2
RT
dt
RT
RT
the higher Ea value is, the more significant of the effect of increasing T on the reaction rate
Concentration
of reactants / products
The effect of increasing a concentration is positive if the respective order is positive

The larger the value of order is the stronger the effect of increasing conc on the rate
When order equals to zero, there is no effect of concentration on the rate.
The
presence of a catalyst
A catalyst can alter reaction rate (speeding up desired rxns or slowing down undesired rxns)
Note: we assume rate of mass transfer (to meet) is sufficient high comparing to rA.
21
Chemical Reactions
The reaction rate and mass transfer rate

When we discuss the reaction rate, it only makes sense if there are sufficient number
reactant molecules can be delivered to the reaction site.
We
say a reaction is kinetic control when the rate of mass transfer > the rate of rxn rA.
This means that molecules being transported
to the reaction site are queuing for reaction
mass
transfer
reaction
If
the mass transfer rate is slower than the reaction rate, the overall rate we observed
will be the rate of mass transfer, not the reaction rate - diffusion control
This means that molecules are waiting to be delivered

before reacting queuing for reaction
The
concept of rate determining step (r.d.s.)
mass
transfer reaction
The slowest step in a reaction process determine the overall rate of a reaction
22
Chemical Reactions
Catalysis and catalysts

Catalyst is a substance which can alter reaction rate without itself being
destroyed or consumed (many other definitions and this is one of them)
95%
of chemical industries apply one or more catalysts in their processes

e.g. polymerisation, air/water depolution, ammonia synthesis, cracking heavy oil to
LPG, etc
catalyst can be an acid, a base; can be a liquid or a solid. Most industrial catalysts
are metals, metal oxides or a mixture of them formulated & made in special ways
Use
of catalysts in industry
Speeding up desired reactions thus increase the process output
Slowing down undesired reaction thus reduce the unwanted waste products
Altering reaction route by changing the relative speed of certain steps in a reaction network
therefore realising certain products which would not be possible without catalysts.
Allowing some rxns to occur under mild conditions e.g. working with heat sensitive materials
Enzymes are catalysts that participate in bio-active processes
etc
23
Chemical Reactions
Calculation of reaction rate

Example: a gas phase reaction 2N2O5=4NO2+O2 occurs at 300C. The concentrations of N2O5 found
in the reaction mixture at different time intervals are given below:
t h
0
1
2
3
5
7
9
[N2O5] mol/L
1.40
1.07
0.80
0.58
0.34
0.18
0.09
Calculate the rxn rates w.r.t. N2O5, NO2 & O2 1) betw. 0-1h; 2) betw. 3-5h; 3) average betw 0-9h.
N2O5 consumption rate
Eqns to use:
1) 0-1 h
rN 2O5
2) 3-5h
rN 2O5
3) aver. rN 2O5
rN 2O5
NO2 formation rate
[A]2 [A]1
; rNO2
t 2 t1
4
2
[A]2 [A]1 ;
t 2 t1
O2 formation rate
rO2
1
2
[A]2 [A]1
t 2 t1
4
1
1.07 1.40 0.165 mol/L h
1.07 1.40
2 1.07 1.40
0.33; rNO2
0.66; rO2 2
1 0
1 0
1 0
4
1
0.34 0.58 0.06 mol/L h
0.34 0.58
2 0.34 0.58
0.12; rNO2
0.24; rO2 2
53
1 0
1 0
4
1
0.09 1.40 0.073 mol/L h
0.09 1.40
2 0.09 1.40
0.146; rNO2
0.291; rO2 2
90
1 0
1 0
24
Chemical Reactions
More about reaction rate
2N2O5 = 4NO2 + O2
1) 0-1 h
rN2O5=0.33
rNO2=0.66
rO2=0.165
mol/Lh
2) 3-5h
rN2O5=0.12
rNO2=0.24
rO2=0.06
mol/Lh
3) aver.
rN2O5=0.146
rNO2=0.291
rO2=0.073
mol/Lh
For
the same reaction, the reaction rate expressed by different components varies
with their stoichiometry coefficients
rN 2O5
rNO2
rO2
2
4
1
Given reaction rate for one of the rxn components you should be able to calc others.
rN2O5 : rNO2 : rO2 = 2 : 4 : 1 or
For the same reaction the reaction rate may vary with the time
because of change of reactant concs with time & rate in general is proportional to [ ]s.
When rxn orders w.r.t. reactant > 0 (usually they are) the rxn rate rbeginning > rlater
As
reaction rate is a function of temperature, the determination of reaction of reaction

rate must be done at a constant temperature (you may need to determine the rate at
a different T, or you may need to vary temperature to determine such as Ea
Dont
forget to put the correct unit to the reaction rate you determined
25
Chemical Reactions
Chemical Reaction Calculations

Question 1.
How many grams of water are produced in the oxidation of 1.0g of glucose,
C6H12O6? Reaction equation: C6H12O6 + 6O2 = 6CO2 + 6H2O
Step 1: Use molar mass of glucose to convert g to moles

1 mole C6H12O6=6x12(C)+12x1(H)+6x16(O)=180g/mol
number of moles C6H12O6=1.0g x (1mol/180g)=5.55x10-3 mol
Step 2: Use balanced equation to determine no. of moles of H2O produced
1 mole C6H12O6 produces 6 moles H2O

the no. of moles of H2O produced: 5.55x10-3 moles C6H12O6x6=0.033 moles H2O
Step 3: Convert moles of H2O to grams using molar mass
1 mole of H2O=2x1(H)+1x16(O)=18 g/mol
Grams of H2O produced: 0.033 mol of H2Ox(18g/mol)x = 0.6g H2O (answer)
Note: You cannot use the weight directly in the calculation. It has to be converted to moles.
26
Chemical Reactions

Question 2.
In a reactor one put 180g of glucose (C6H12O6) and 160g of O2. Can you
produce 108g of H2O. Why? What is the maximum amount of H2O which can
be produced? Reaction equation: C6H12O6 + 6O2 = 6CO2 + 6H2O
Step 1: Convert all components from grams to moles:

No.moles of C6H12O6=180g/190g/mol=1 mole of C6H12O6
No.moles of O2= 160/32g/mol=5 mole of O2
No.moles of H2O= 108/18g/mol=6 mole of O2
Step 2: Find out how much glucose AND O2 you need to produce 108g H2O.
To produce 108g which is 6 moles of H2O, you will need 1mole glucose AND 6 moles of O2.
Do we have enough glucose? - Yes. Do we have enough O2? - No.
Step 3: Every 6 molecules of O2 will burn 1 molecule of glucose, this will proceed UNTIL
one of the reactant consumed completely, in this case O2.
When all O2 is consumed the reaction will stop and the max. amount of H2O which can be
produced can be calculated from O2 available: 5moles of O2 gives 5moles (or 90g) of H2O
Note: When one of reactants is consumed completely the reaction will stop.
27
Chemical Reactions

Question 3.
As in Question 2, one puts 180g of glucose (C6H12O6) and 160g of O2. When
O2 is completely consumed, what is the glucose left & what is the percentage
conversion of glucose? Reaction equation: C6H12O6 + 6O2 = 6CO2 + 6H2O
Step 1: Convert all components from grams to moles:

No.moles of C6H12O6=180g/190g/mol=1 mole of C6H12O6
No.moles of O2= 160/32g/mol=5 mole of O2
No.moles of H2O= 108/18g/mol=6 mole of O2
Step 2: Find out how much glucose left after all O2 has consumed.
The molar ratio of glucose and O2 in the reaction=1:6. For a consumption of 5 moles of O2,
the amount glucose reacted will be 1x5/6=5/6 moles or 0.83 moles, or 0.83x180=150g.
The amount glucose left over=1-0.83=0.167moles or 180-150=30g
Step 3: The percentage conversion of glucose at complete conversion of O2
conversion(%)
[A]in [A]out
1 0.833
100 %
100 % 83 .3%
[A]in
1
(try the weight base)
Note: The conversion (%) calculated based on moles is the same as that based on weight .
28
Chemical Reactions

Question 4.
The brown gas NO2 can form colorless gas N2O4, 2NO2 D N2O4. At 25C the
concentrations of NO2 & N2O4 are 0.018 M & 0.055 M respectively when at
equilibrium. 1) Calculate the equilibrium constant Keq at 25C. 2) If in another
equilibrium system of the same gases at the same temperature, the NO2
concentration is found to be 0.08 M, what is the concentration of N2O4?
Step 1: Determine the equilibrium constant

From equilibrium constant definition:
K eq
[N 2 O 4 ] 0.055
170
2
2
[NO 2 ]
0.018
Step 2: When at equilibrium
[N 2 O 4 ] [N 2 O 4 ]
2
K eq
170
[N
O
]
0.08
170 1.088 M
2 4
[NO 2 ]2
0.08 2
29
Chemical Reactions

Question 5.
The rate constants of a reaction are determined to be 3x10-5 mol/L.h at

200C and 4x10-4 mol/L.h at 250C. Estimate the reaction activation
energy.
Arrhenius eqn relates the rate constant to activation energy
ln k
Mthd.1: lnk=lnA0+(-Ea/R)(1/T), A plot of lnk against 1/T will produce a
k A0 e Ea / RT
slope= -12750
straight line, the slope of which is -Ea/R. So that Ea=slope x R

E =-12750 x 8.314=106,000 J/mol = 106 kJ/mol
k1a A0 ,1e Ea / RT1 & k 2 A0 ,2 e Ea / RT2

Mthd 2: k
A0 ,1e Ea / RT1
A0 ,1e Ea / RT1
k1
1
ln ln
Ea / RT2
Ea / RT2
k 2 A0 ,2 e
A
e
0
,
2
k2
1/T
A Ea Ea
ln 0 ,1
A RT RT
2
0 ,2 1
Ea Ea T1 T2
RT1T2 k1
a

or Ea
ln 1
ln
k
RT
RT
RT
T
T
T
1
2
1 2
1
2
2
k2
Let A0,1
=A0,2 E
k
T1=273+200 K, T2=273+250 K, k1=3x10-5 & k2=4x10-4 mol/L.h,

R=8.314 JK/mol
5
RT1T2 k1 8.314 273 200273 250 3 10

106 kJ/mol
Ea
ln
ln
4
273 200 273 250 4 10
T1 T2 k2
30
Chemical Reactions

Question 6.
Answer:
Two catalysts A & B are compared for their catalytic activity for reaction RP.
When A is present it takes 10s for R to change from 2 to 0.5 moles and when
B is present it takes 20s for R to decrease from 5 to 2 moles at the same
temperature and with the quantities of catalyst.
Which catalyst is more active for the reaction concerned?
The activity of two catalysts can be compared based on the average reaction
rate when A & B presence separately.
rR ,A
rR ,B
[ R]2 ,A - [ R]1,A 0.5 - 2
0.15 mol/s
Dt A
10
[ R]2 ,B - [ R]1,B 3 - 5
0.10 mol/s
Dt B
20
The A catalyst is more active for the reaction concerned.
31
Chemical Reactions

Question 7.
Answer:
Verify that the rate constant of a reaction following second order rate law
rA=-k[A]2 can be determined from the slope of a line obtained by plotting 1/[A]t
against reaction time t, where [A]t is the concentration of A measured at time t.
d [A]
k[A]2
Second order rate law:
dt
d [A]
d [A]
2
k
[A]
kdt
rearrange:
dt
[A]2
rA
(1)
(2)
Define boundary conditions: at t=0, [A]=[A]0 and at t=t, [A]=[A]t

integrate eqn (2), t from 0-t and [A] from [A]0 to [A]t
[A]t - 1
t
1 1
d [A]
1
1
kdt
d
[A]
k
dt
k
t
kt
[A]0 [A]2
0
[A] [A]
[A]2
[A]t
[A]0
t 0
(3)
compare eqn (3) with linear eqn Y=aX+B, which is a straight line with slope a
1
1
, a k , X t and b
[A]t
[A]0
1
A plot of [A] vs. t will give a straight line with slope=k.
t
Let
1/[A]
slope=k
32
Chemical Reactions

Question 8.
Answer:
Reaction RP follows the second order rate law rR=-k[R]2. Verify that the time
required for the reactant R to fall to a half of its initial value is t1/2=1/(k[R]).
Second order rate law:
rR
d [R]
k[R]2
dt
(1)
After integration of eqn (1) with the boundary conditions:

at t=0, [R]=[R]0 & at t=t1/2, [R]=[R]t1/2=0.5[R]0
1
1
1
1
kt
kt1 / 2
[R]t
[R]0
0.5[R]0
[R]0
1
1
1 1
1 1 2
1

kt1 / 2
t1 / 2
0.5[R]0 [R]0
k 0.5[R]0 [R]0 k [R]0 [R]0
1
t1 / 2
k[R]0
33
Chemical Reactions
Homogeneous and Heterogeneous Reactions
In a chemical reaction, the reactants can be in various physical states
Homogeneous - All of reactants & products in the same phase & no phase boundary
Heterogeneous - Involving multi-phases & phase boundary crossing

Phase
gas - gas
Type
Homog.
Example
2NO + O2 = 2NO2
gas - liquid
Hetrog.
CO2 + H2O = H2CO3
gas - solid
Hetrog.
O2 + Fe = Fe2O3
liquid - liquid (miscible)*
Homog.
NaOH + HCl = NaCl + H2O
liquid - solid
Hetrog.
CaO + H2O = Ca(OH)2
solid - solid
Hetrog.
CaCO3 = CaO + CO2
* When two immiscible liquid, such as oil and water is regarded as heterogeneous type.
34
Chemical Reactions
Phase & Phase Change

A substance can exist in different physical states
Solid
Energy level
The temperatures at which phase changes occur

vary with substances and circumstances (e.g. P)
solid
The energy required for phase change varies with

substances and type of phase change.
The energy possessed by molecules of the same
substance at different state are different
water
vapour
Temperature
liqui
d
freezing
Note: Some other states may sometime mentioned.

such as liquid-crystal, super-critical state, gel. etc.
sublimation
Liquid
evaporation
deposition
Gas / vapour
condensation
gas
melting
liquid
water
evaporating
ice melting
Energy (heat) added
35
Chemical Reactions
Reactions In Liquid Phase - Solution
Solution = solute + solvent
solute - substance that is dissolved

solvent - dissolving medium
Solute
is a solid or a gas - solute is dissolved in solvent (e.g. NaCl + H2O, O2 + H2O)
Solute
is another liquid - solute and solvent are miscible (e.g. C2H6O + H2O)
solute in a solution can exist as molecules or ions, or both (such as weak acid)
some solutes are dissolved in a solvent in any proportions (e.g. C2H6O in water); others are
only dissolved in a solvent in certain proportion - solubility limitation (e.g. NaCl or N2 in H2O)
Concentration of a solution - the amount of solute in the solution

Molar
concentration (molarity) - number of moles solute in ONE litre solution
Molarity is the most commonly used concentration unit in chemistry
Weight
percentage (wt.%) of solute in solution
definition: solute wt%=100% x (wt of solute)/(wt. of solute + wt. of solvent)

e.g. A solution contains 20g solute & 30g solvent
solute wt%=100% x 20/(20+30)=40wt%
(the wt% of solvent =100%-40%=60%)

36
Chemical Reactions
Reactions In Liquid Phase - Solution
Some important notes on the chemical reaction in solution
When a solute dissolve in solution, solute can either be present as molecules or ions
as molecules. e.g. dissolving sugar in water - not electronic conductivity.
as ions. e.g. dissolving salt (NaCl) in water - Na+ & Cl- both conduct electricity.
Strong acids or base, when dissolved in H2O, form only ions in solution
Weak acid or base, when dissolved in H2O, form mixture of molecules and ions (partial dissociatn)
The solubility of some gas solutes, when dissolved in a solvent, depends on the
pressure of the solute gas above the solution
ideal solution: Pi=xiPi* or xi=Pi / Pi*
in which
Pi - vapour pressure of solute i

xi - mole fraction of solute i in solution
Pi* - equil. vapour pressure of pure solute i
Solvent molecules may form weak bond with solute molecules (e.g. Hydrogen-bond),
which may to a certain degree change the reactivity of solute.
The presence of solute may affect certain properties of the resultant solution
e.g. boiling point elevation, freezing point depression, osmosis pressure, etc.
37
Chemical Reactions
Gas Phase Reactions
Distinctive features of molecules in gas phase in relation to reaction
Having high energy
Moving freely within the space of reaction
High mass transfer rate - General magnitude of mass transfer rate in solid, liquid and gas
solid 100
liquid 103
gas 105
High heat transfer rate - This is very important for reactions involving heating/cooling
In practice, many reactions in which the reactants are liquid or solid at normal temperature
are carried out at elevated temperatures in order to convert the reactants to gas
Compressible therefore sensitive to the reaction pressure
Sometime a liquid or even a solid substance is heat to gas phase to react

e.g. steam reforming hydrocarbons, heavy oil cracking,
This has implication on the reactions involving the change of number of moles before and
after reaction.
The main disadvantages of the gas phase reactions are
Usually high volume (large reactor)
not suitable for heat sensitive substances if heating to high temperature is required.
38
Chemical Reactions
Solid Phase Reactions
Solid phase reactions are usually slow due to limited mobility of molecules
When a solid reacts with another reactant which is liquid or gas, the
reaction starts from outer surface of the solid
In industry if a reaction involves a solid reactant (at ordinary temperature)

what we usually do is
dissolving
heating
solid in solvent
it to above the melting point so that it takes part in reaction as a liquid
Many catalytic reactions use solid catalysts

The
reactant in this case can be a liquid or a gas or liquid-gas mixed phase
Solid
It
catalysts are very easy to separate from liquid, gas or a liquid-gas mixture
is easy to handle solid catalysts from practical point of view (loading, discharge etc)
39
Chemical Reactions
Reactions involve multi-phases
Many reactions involve multi-phase in one reactor
reactants and products can be presented as any combination of two or three phases.
When multi-phases present in a rxn following issues become important:
Relative rate of reactant and/or product molecules diffusion within each phase as well
as through phase boundaries must match the rate of reaction
Solubility of solids and/or gases in liquid phase
When a porous solid is involved the liquid/gas molecules transport within the pore
Both pressures (for gas phase) and concentrations (for liquid) are interlinked in the
reaction network therefore these have to be considered systematically.
When reaction involves heating or cooling, as most of reactions do, this has to be
dealt with by considering both mass transfer and heat transfer within and between
different phases.
The main advantage of multi-phase reactions is the easiness for separation

40
Chemical Reactions
Example of Reactions involving multi-phases

The long journey for reactant molecules
j. travel within gas phase
gas phase
reactant molecule
k. cross gas-liquid phase boundary

l. travel within liquid phase
gas phase
m. cross liquid-solid phase boundary

n. reach outer surface of solid
o. travel with pore
k
l
liquid
phase
mn
p. reach reaction site

o
q. be adsorbed on the site and activated

r. react with other reactant molecules (either
adsorbed or approached from surface above
Product molecules must follow the reverse
process to return to gas phase
porous
solid
pore
pq r
Heat transfer follows similar process

41
Chemical Reactions
Acids and Bases
Acids & Bases are one of the most important classes of chemicals
Acids and bases have been know to human for a long time
Acids taste sour (in fruit), change colour of certain dye
Bases taste bitter and feel slippery (like in soap, lime water)
Acids and bases are widely present in nature,
especially in plants, electrolyte balance in life system cycle etc
Acids and bases are widely used in industry for various purpose
Dissolving chemicals, e.g. HF, aqua regia (HCl:HNO3=3:1)
Reagents for producing various chemicals
Catalysing various types of reactions
Titration in volumetric analysis
etc
42
Chemical Reactions
Acids and Bases - Definition
Classical definition
Acids - Substances that, when dissolved in water, increase the concentration of H+ ions
e.g.
HCl(g)
H2O
H+(aq) + Cl-(aq)
Note: H+, which is a proton only (no e- ), is actually bond with water molecule forming H3O+, the rxn is
HCl(g) + H2O (l) H3O+(aq) + Cl-(aq)

For simplicity, we often use H+ instead of H3O+.
-
Bases - Substance that, when dissolved in water, increase the concentration of OH ions
e.g.
NaOH
H2O
OH-(aq) + Na+(aq)
NH3 + H2O NH4+ + OH
Brnsted-Lowry definition
Acid is proton donor and Base is proton acceptor
-
(because H+ is a proton and OH of a base reacts with H+ giving water)

43
Chemical Reactions
Conjugate Acid and Base Pairs
An acid & a base always work together to transfer proton (donate-accept). A substance
can function as an acid only if another substance behaves simultaneously as a base.
When an acid or a base is dissolved in water, ions are released - this process involves
proton transfer. To mark the process and link the ions with its original acid or base,
conjugate acid-base pairs are defined.
remove H+
HX(aq) + H2O (l)

acid
Acid
base
X-(aq)
conjugate base
add H+
H3O+(aq)
conjugate acid
and conjugate base always appear in pair; likewise base and conjugate acid appear in pair
an acid losses proton (H+) it becomes the conjugate base of that acid (e.g. HX to X -)
when a base receives a proton (H+) it becomes the conjugate acid of that base (H2O to H3O+)
If an acid dissolves in water, H2O is a base; if a base dissolves in water, H2O becomes an acid.
When
add H+
remove H+
HCl(aq) + H2O(l) Cl-(aq) + H3O+(aq)

acid
base
conjugate
base
add H+
conjugate
acid
NH3(aq) + H2O(l) NH4+(aq) + OH-(aq)

base
acid
conjugate conjugate
acid
base
remove H+
44
Chemical Reactions
Strengths of Acids and Bases
The strength of acids and bases
acids, paired with bases with negligible basicity
- Able to completely transfer their proton to water
Weak
acids, paired with week bases
- These acids are partially dissociated to ions

- Their conjugate bases are also weak, with limited ability of
accepting proton
Acids with negligible acidity, paired with strong bases
- Their conjugate bases, however, are strong bases

Water can act as acid as well as base
strong
- These class of acids, though carrying H, give out no [H+]
negligible
base
Cl
HSO4
NO3
H2O
2SO4
H2PO4
F
C2H3O2
HCO3
HS
2HPO4
NH3
2CO3
3PO4
OH
2O
H
CH3
weak
- Their conjugate bases are the weakest, with negligible

tendency to accept proton
acid
HCl
H2SO4
HNO3
H3O
HSO4
H3PO4
HF
HC2H3O2
H2CO3
H2S
H2PO4
NH4
HCO3
HPO4
H2O
OH
H2
CH4
base strength increase
Strong
weak
Common acids and their relative strengths

acid strength increase
strong
strength of an acid is the ability to donate proton,

or increase [H+] when acid is dissolved in water.
likewise, the ability to accept proton, or [OH-],
determine the strength of a base
negligible
The
45
Chemical Reactions
Acid and Base Equilibrium
The extent of ionisation of an acid or a base in water
Some acids (or bases) ionise in water completely, leaving no molecules behind
Other acids (or bases) ionise partially in water, forming an equilibrium between
molecules and ions
e.g.
HF(aq) + H2O (l) D F-(aq) + H3O+(aq)
(1)
NH3(g) + H2O (l) D NH4+(aq) + OH-(aq)
(2)
The tendency of ionisation of an acid (or a base) varies with the type of acids, we
can use the concept of reaction equilibrium to indicate the degree of ionisation.
The equilibrium constant used to describe the degree of ionisation of an acid is
called acid-dissociation constant, Ka, which is defined as
for equili. (1)
for equili. (2)
ions
[F - ][H 3O ]
[F - ][H ]
K a K eq
or K a
molecule
[HF]
[HF]
[NH4 ][OH ]
K a K eq
The higher the Ka value, the higher
[NH3 ]
ion conc., the higher acidity/basicity
46
Chemical Reactions
Quantifying the Strength of Acids and Bases

[H+] and [OH-] are the measure of the strengths of acids and bases
We know that an acid when dissolved in water releases [H+] and a base gives [OH-]
We also know that the strengths of an acid or a base depend on the [H+] and [OH-]
It comes naturally that [H+] & [OH-] are used to indicate the strengths of acids/bases
The range of [H+] and [OH-]
Dilute aqueous solutions at 25C always give,

Kw=[H+][OH-]=1.0x10-14
For an acid [H+]>[OH-], Kw=[H+][OH-]=1.0x10-14
For a base [OH-]>[H+], Kw=[H+][OH-]=1.0x10-14
For pure water, which is neutral
[H+]=[OH-]=1.0x10-7, Kw=[H+][OH-]=1.0x10-14
pH scale
water can act as an acid as well as a base

at equilibrium
H2O D H+ + OHEquili. constant at 25 C is found to be
[H ][OH ]
Kw
[H ][OH ] 1.010-14
[H2O]
Further examine other aqueous solution

the same relation holds
Known [H+], [OH-] can be calculated by this eqn.
In pure water [H2O] is constant
For convenience the low value of [H+] and [OH-], we use the scale of log10 [H+]
define pH= -log10[H+] Scale: 1-14. Acid pH=0-7 [H+]>[OH-]; strong acids have low pH
Base pH=7-14 [OH-]>[H+]; strong bases have high pH
Note: When using [OH-] (which is less used), we have pOH= -log10[OH-] (=14-pH)
47
Chemical Reactions
Calculation of pH
Example 1: Calculate pH of 0.05M HNO3 solution
HNO3 + H2O H3O+ + NO3HNO3 is a strong acid, HNO3 ionizes completely in water, i.e. [H3O+]= 0.05M
pH = - log10[0.05] = 1.3
Example 2: Calculate pH and pOH of 0.05M NaOH solution

NaOH + H2O Na+ + OHNaOH is a strong base, NaOH ionizes completely in water, i.e. [OH-]=0.05M,
Kw = [H3O+][OH-] = 1 x10-14 M2
[H3O+] = 1 x10-14 M2 / [OH-] = 1 x10-14 M2 / 0.05 M = 2 x 10-13 M
pH = - log10[2 x 10-13] = 12.7

pOH = 14 - pH = 14 - 12.7 = 1.3
(why is this result the same as that of example1?)
48
Chemical Reactions
Calculation of pH
Example 3: What is the [OH-], in mol/L, in a solution whose pH is 9.72?
Known: pH = - log10[H3O+] = 9.72 [H3O+] = 1.9 x 10-10 (mol/L)
for any aqueous solution
Kw = [H3O+][OH- ] = 1.0 x 10-14 (mol/L)2
[OH- ] = Kw / [H3O+] = 11.0 x 10-14 (mol/L)2 / 1.9 x 10-10 (mol/L) = 5.3 x 10-5 (mol / L)
Example 4: The acid-dissociation constant, Ka, of hydrofluoric acid is 6.8x10-4. What is

the [H3O+] in a 2M HF solution? What is the pH of the solution?
HF(aq) + H2O (l) D F-(aq) + H3O+(aq)
initial
at equili.
2
2-x
[F ][H 3O ]
xx
6.8 10 4
[HF]
2- x
Solve the eqn for x ( = [H3O+])
x 2 6.8 104 x 2 6.8 104 x 0.0365 M
By definition K a K eq
pH = - log10[H3O+] = - log10(0.0365) = 1.44

49
Chemical Equilibria
Aqueous Equilibria and Some Applications
In chemistry many aqueous systems involve equilibria
Human body fluids are in electrolyte equilibria in order to function properly
Electrolyte: aqueous solutions that contain ions
Plants contain weak acids, which maintain right balance for plants to grow
Many properties of a solution that has ions are affected by its equilibrium state.
etc. (In a broad sense, harmony=balance=equilibria)
Many phenomena in chemistry can be studied by means of equilibria.

We will look at:
The behaviour of an equilibrated electrolyte solution when other ions are added
Applications
Buffer effect
Acid-base titration
Solubility of ionic substances and the factors affecting it

50
Chemical Equilibria
The Common-Ion Effect from Equilibrium
Considering the following two cases

Case 1. What is the pH of 0.3M acetic acid HC2H3O2 solution, (Ka=1.8x10-5)?
HC2H3O2(aq) D H+ (aq) + C2H3O2-(aq)
initial
0.3
at equilibrium
0.3-x
By definition
[H ][C2 H3O-2 ]
xx
Ka
1.8 105
[HC2 H3O2 ]
0.3- x
Solve eqn for x
x [H ] 2.3 10 3 M
pH -log[H ] -log 2.3 10 3 2.64
Note: HC2H3O2 is a weak acid (Ka<<1) and the water solutn of HC2H3O2 is an electrolyte solution.
51
Chemical Equilibria
The Common-Ion Effect from Equilibrium
(contd)
Case 2. What is the pH of solutn contains 0.3M acetic acid HC2H3O2 & 0.3M NaC2H3O2?
HC2H3O2(aq) D H+(aq) + C2H3O2-(aq)
initial
0.3
at equilibrium
0.3-x
0.3+x
[H ][C2 H3O-2 ] x 0.3 x
1.8 105
By definition K a
[HC 2 H3O2 ]
0.3- x
Solve equ for x
x [H ] 1.8 10 5 M
pH -log[H ] -log 1.8 10 5 4.74
Note: C2H3O2- is the conjugate base

of HC2H3O2
Note:
NaC2H3O2 ionises in water completely
NaC2H3O2(aq) D Na+(aq) + C2H3O2-aq)
Note: The presence of NaC2H3O2 &

Na+ does not change Ka value
Compare cases 1 & 2:

The extent of ionisation of HC2H3O2 is reduced by the presence of NaC2H3O2 (which has
C2H3O2- ion in common with HC2H3O2)
This is called the Common-ion Effect. It works in many equilibrated electrolyte solutions
such as buffer solutions, solubility of ionic compounds etc.
52
Chemical Equilibria
Buffered Solutions
Behaviour of a solution containing a weak conjugate acid-base pair

equilibrium of weak acid
HX(aq) D H+(aq) + X-(aq)
acid-dissociation constant
[H ][X - ]
[HX]
Ka
[H ] K a
[HX]
[X - ]
If a base, OH-, is added,
OH-(aq) + HX(aq) D H2O(aq) + X-(aq)
[HX] & [X-]
If an acid, H+, is added,
H+(aq) + X-(aq) D HX(aq)
[X-] & [HX]
As the HC2H3O2 and

C2H3O2- pair in case 2
When the addition of OH- or H+ is small compared to [HX] & [X-], the change to [HX] & [X-] is very
small, so does the ratio [HX] / [X-] the [H+] thus pH will remain almost constant.
A Buffered Solution (also called Buffer) contains a weak conjugate acid-base

pair. It can resist drastic change of pH upon the adding strong acid or base.
Buffers solutions are widely used in biology and biochemistry because of the
need of maintaining certain pH for some reactions/process to occur properly.
Note: Buffer solutions can be made for all pH ranges. The amount of acid or base it can
neutralise before pH begins to change (called buffer capacity) depends on the [HX] & [X-].
53
Chemical Equilibria
Solubility of Ionic Compounds
Equilibrium between solid of ionic compound and its ions when dissolved
dissolving
CaCO3(s) D Ca2+(aq) + CO32-(aq)

precipitation
Equilibrium constant:
Note: The solid CaCO3 does not

appear in the expression
solubility-product constant Ksp=[Ca2+] [CO32-]
When adding another strong electrolyte Na2CO3, which dissociates completely in

water solution and contains common ions CO32-, into the above equilibrated solution
The above equilibrium will shift to the left, meaning that the CaCO3 solubility
Reason? - Common-ion effect (Ksp is constant, [CO32-] [Ca2+] [CaCO3] )
Addition of common ions alter the equilibrated solubility of an ionic compound.

(you may like to link this with the cases such as scale formation in kettle, kidney stone, etc.)
54
Chemical Equilibria
Solubility of Ionic Compounds
Equilibrium between solid and its constituent ions containing OHdissolving
Mg(OH)2(s) D Mg2+(aq) + 2OH-(aq)

precipitation
Many metal hydroxides are partially dissolved in solutn (or precipitated when formed)
solubility-product constant Ksp=[Mg2+] [OH-]2
Note: the stoichiometric number raised

to power in Ksp expression
When adding an acid, H+, into the above equilibrated solution, a reduction of solution
pH occur due to the following reaction: H+ + OH- D H2O, OH- in the solution is
consumed thus reduced [OH-] [Mg2+] [Mg(OH)2] .
This is also a kind of common-ion effect but working in reverse direction.

Due to consumption of one of ions in the equilibrated solid-ions solution, the
equilibrated solubility of an ionic compound is increased.
(you may like to link this with the cases such as kettle de-scaling, tooth decay etc.)
55
Chemical Applications
Titration
A method to determine the concentration of a particular solute in a solution
Titration reactions
Acid base reactions (acid / base indicators, etc)

Oxidation-reduction reactions (colour change, etc
Precipitation (cloud appearance, etc)
Standard solution - a solution with known concentration which is used to titrate.
Equivalent point - The point at which stoichiometrically equivalent quantities are

brought together. It is a theoretical point of reaching stoichiometry
End point - The point at which a pre-determined indication of reaching the equivalent
point effects. It is practically the point one stops adding standard solution
and is usually very close to the Equivalent point
Usual means of indicating the arrival at the end point
Colour (indicators or the colour change of the substance itself before and after equiv. point
Conductivity if the quantities of ions is used as an indication
Others such as precipitation formation
56
Chemical Applications
Acid - Base Titration
Typical titration curves of strong

& weak acids by Strong base
pH change of weak acids is less

drastically as that of strong acids
because of equilibrium shifting
Typical titration curve of polyprotic

acids by Strong base
Different equilibria of ions with

different charges
pH
14
pH
14
Equivalent point
12
12
Ka=10-10
10
Ka=10-6
Ka=10-4
HPO3 2-
10
Ka=10-8
Ka=10-2
H3PO3
H2PO3-
2
0
0 10
strong acid
20
30 40 50
mL NaOH
60
0
0
20
40
60 80
mL NaOH
100
57
Chemistry for Life
Introductory to Organic Chemistry
Organic chemistry
A branch of chemistry devoted to the study of carbon-containing (organic) molecules

All life forms on earth have organic molecules as their basic building blocks
The most important carbon-containing molecules are hydrocarbons (HCs)
General characteristics of hydrocarbons (HCs)
Hydrocarbons (HCs) - molecules contains mainly carbon (C), hydrogen (H)

Bonds and general structures
The bonds of HCs are mainly covalent, formed between C and C (C-C, C=C or CC), H (CH), O (C-O or C=O) and others such as N (C-N).
The C-C bonds forms the backbone or skeleton of HCs and Hs are at surface
Functional groups (FGs)
Many FGs attached to C-C skeleton give HCs various unique function and properties.
Stability
All HCs can burn in oxygen easily giving heat.
C-C single bonds are most stable (- > = > ), C-H & C-FGs are easy to break
58
Chemistry for Life
There are four types of HCs (based on the kinds of C-C bonds)
Alkanes (C-C)
Alkenes (C=C)
contain C=C bonds
Alkynes (CC)
contain only C-C bonds in this group of molecules, also called saturated HCs
contain CC bonds
unsaturated HCs
Aromatics
carbon atoms are connected in a planar ring structure
usually possess special odour
59
Chemistry for Life
Alkanes
Most stable HCs
Its molecular formula can generally be written as CnH2n+2, where n is the number of
carbon atoms in molecule.
Most common alkanes
Name
Molecular
formula
methane
CH4
ethane
C2H6
propane
C3H8
butane
C4H10
pentane
C5H12
Condensed
structure formulary
Lewis structure
H
CH4
H-C-H
H H
H
H-C-C-H
CH3CH3 or CH3-CH3
H HH
H H
H-C-C-C-H
CH3CH2CH3
H HH
H HH H
CH3CH2CH2CH3
H-C-C-C-C-H
H HH HH
H HH H
CH3CH2CH2CH2CH3
H-C-C-C-C-C-H
H HH HH
Boiling
point
-161C
-89C
-44C
-0.5C
36C
60
Chemistry for Life
Some general points about HCs
Straight-chain HCs: All carbon atoms are joined in a non-branched chain

C-C
-C-C-C-C-
C-C-C-C-C=C-C-C-C
Branched-chain HCs
-C-C-CC
C-C-C
-C-C-C
C
Structural isomers
compounds that have the same
molecules formulas but with
different bonding arrangement
C
C-C-C-C-C=C-C-C
C
C-C-C-C-C=C
C
C
C
C-C-C-C-C=C
C-C-C-C-C=C
CAll
C of these are isomers ofCC9H18C
There is a system way of naming HCs

to differentiate the isomers with different structures
We can sometimes write only carbon atoms to show the structure & bonds, as
shown above
61
Chemistry for Life
Alkenes
Less stable than alkanes
Its molecular formula can generally be written as CnH2n, where n is the number of
carbon atoms in a molecule.
The double bond C=C can locate between any two C (n equal to or larger than 2).
There can be more than one double bonds in an alkene
Isomers exists when n equal or larger than 4.
Common alkenes
ethene or ethylene
CH2=CH2 or CH2CH2
(ethene is a plant hormone)
propene or propylene
CH3-CH=CH2 or CH2CHCH2 (play key role in fruit ripening)
62
Chemistry for Life
Alkynes
Least stable - very active
It molecular formula can generally be written as CnH2n-2, where n is the number of

carbon atoms in molecule.
The triple bond CC can locate between any two C (n equal to or larger than 2).
There can be more than one triple bonds in an alkyne
Isomers exists when n equal or larger than 4.
Common alkenes
acetylene
CH CH or CHCH
very active. Burn in oxygen - oxiacetylene torch

with flame temperature 3200K.
Very important intermediates in chemical industry
63
Chemistry for Life
Aromatic HCs
More stable than alkenes and alkynes, though there are unsaturated bonds.
Most common aromatic HC is benzene
Examples of other aromatic compounds
H
C
H
C
H
C
or
CH3
H3C
H3C
H3C
C
C
H
CH3
CH3
HO
Tuluene
Cholesterol
64
Chemistry for Life
Some common functional groups

Alcohols
R-OH
R-O-R
O
R-C-H
O
R-C-R
O
R-C-OH
O
R-C-O-R
O
R-C-N-R
(name suffix -ol)
Soluble in H2O; use in food, medicine, cholesterol is an alcohol

Ethers
(name suffix ether)
Mostly used as solvent

Aldehydes
(name suffix -al)
Flavour (vanilla, cinnamon etc)
Ketones (name suffix -one)

Such as acetone used extensively as solvent
Carboxylic
acids (name suffix -oic acid)
Sour veg, fruits; application in polymers, fibres, paints

Esters
(name suffix -oate)
very pleasant odour (fruits)

Amines
and Amides (name suffix -amide)
Are key functional group in protein structure

65
Chemistry for Life
Introductory to Biochemistry
Some general remarks on Biochemistry
Biochemistry - Biological chemistry which studies living species in chemical means
Looking at the compositions and structure of biochemical molecules, and try to understand
their functions at molecular level.
Looking at the properties these molecules especially from biological point of view
The change processes of these molecules in relation to its role in life cycle
Making use of our knowledge for human benefits
General observations on biochemical molecules
The molecules are generally very large, molecular wt in the range of 1,000s -1,000,000s
They are generally very complicated in structure, yet they contains mainly C, O, H as their
main building blocks and some other atoms such N, P, S in their functional groups
The specific ways of these molecules are structured make them specific functions in
biological processes.
All life processes of mammals and other animals on the Earth require energy (processes of
bio-molecule synthesis are endothermic in large), which, ultimately coming from the Sun,
are obtained indirectly through plant photosynthesis.
66
Chemistry for Life
- Proteins
Proteins and Amino acids
Proteins are big molecules present in living cells (~50% dry wt of our body)
animal tissues, skin, hair, nails, muscles
All proteins are chemically similar
All proteins are composed of the same building blacks - a-amino acids
HO
HO
H2N-C-C-OH
or
+H N-C-C-O3
R
R
a-amino acids are linked by amide groups, which is formed by reaction between
H
O
-C-O- and H-N- groups of 2 amino acids after dropping a H2O, into proteins
amide group
H
HO HO
HO
HO
+H N-C-C-N-C-C-O- + H O
+H N-C-C-O- + +H N-C-C-O- =
e.g.
2
3
3
3
R
H R
67
Chemistry for Life
Proteins
Structure of proteins - 4 levels
Primary structure - amino acids sequence
Secondary structure - a-helix
Tertiary structure - folded individual peptide
Quaternary structure - aggregation of 2 or more peptides
68
Chemistry for Life
Enzymes
Proteins
Enzyme is one of the most important classes of proteins. Each enzyme is capable
of catalysing very specific reactions with living organisms
More about amino acids
There are many different amino acids, the difference being the R groups
HO
H2N-C-C-OH
e.g.
HO
HO
H2N-C-C-OH
H2N-C-C-OH
Our body requires 20 amino acids
CH3
Glycine
Alanine
Our body can synthesise 10 of these 20
The other 10 (called essential amino acids) must be ingested.
69
Chemistry for Life
Carbohydrates
Carbohydrates (hydrate of carbon)
It has general formula of Cx(H2O)y
It is a form of sugar used for store energy by plants
Carbohydrates can be divided according to the number of units of basic sugar
Monoaccharides - containing a single unit of sugar (that cannot be broken by a acid)

The most important monoaccharides are glucose and fructose
Glucose - the most abundant carbohydrate, C6(H2O)6 or C6H11OH (aldehyde sugar)
Fructose - present in most of fruit, C6(H2O)6 or C6H11OH (ketone sugar)
Diaccharides - composed of two monoaccharides

The most most important diaccharide is sucrose and lactose
Sucrose (table sugar) - is a sugar composed of 1 glucose + 1 fructose.

The invert sugar (sweeter than sucrose) is made from hydrolysis of sucrose converting part of
glucose to fructose. The sugars made from sugar beets and canes are the same.
Lactose (milk sugar) - is a sugar composed of 1 glucose + 1 galactose
Polyaccharides - composed more than two units of monoaccarides

70
Chemistry for Life
Carbohydrates
Some of most important polyaccharides
Starch
Many crops contains mainly starch (corn, potatoes, wheat, rice etc). It is a major way
plants store their energy
It consists of mainly glucose. due to different way in which glucose units are joined
together, starch may be unbranched or branched in structure
Hydrolysis of starch, catalysed by enzyme within our digestive system, gives glucose
Glycogen
These type of polyaccharides can be synthesised within our body and stored in liver and
muscles. It services as immediate energy source of our body.
Cellulose
It forms major structural unit of plants (e.g. wood 50%, cotton fibres 100% cellulose).
usually unbranched chain of glucose units with average molecular weight 500,000 amu.
The enzymes within our body which help hydrolysis starch cannot digest cellulose.
71
Chemistry for Life
Nucleic Acids
Functions of nucleic acids

Nucleic acids are chemical carriers of an organisms genetic information
They are also chemical controller of cell development through controlling protein
synthesis
Composition of nucleic acids
The nucleic acids are bio-polymers (molecules are linked together through
polymerisation reaction like the formation of proteins from amino acids)
The basic building blocks of nucleic acids are called necleotides.
nucleotides are formed from the following units:
1. a phosphoric acid molecule, H3PO4
2. a five-carbon sugar
3. a nitrogen-containing organic base
Type of Nucleic acids
DNA
RNA
72
Chemistry for Life
DNA & RNA
DNA - Deoxyribonucleic Acids
DNA has huge molecular weight ranging from 6~16 million amu
DNA is found primarily in the nucleus of living cell
DNA stores the genetic information of the cell & controls the production of protein
RNA - Ribonucleic Acids
RNA has smaller molecular weight ranging from 20,000~40,000 amu

RNA is mostly found outside the nucleus in the cytoplasma (substance around cell
membrane)
RNA carries the information stored by DNA out of nucleus of cell into cytoplasma,
where proteins are synthesised based on the instruction delivered by RNA
The differences in composition of DNA and RNA
The only difference between DNA and RNA

is the 5-carbon sugar units in the nucleotides.
DNA has deoxyribose
NRA has ribose
HOCH2
H
O
l
l
C
C
Hl
l Hl
l OH
HC
C
l
l
OH OH
ribose
HOCH2
H
O
l
l
C
C
Hl
l Hl
l OH
HC
C
l
l
OH H
deoxyribose
73
Analytical Techniques
Atoms & molecules can have different

states each having a specific E level
n=2
Ground state
Excited state
When absorbing electromeganetic radiation
(e.m.r.). Atoms/molecules rise their E levels
Atoms/molecules at excited state are not stable

& tends to return to their ground state.
In the process of returning their ground states,
the energy gained earlier is release in a form of
e.m.r. (photons).
n=4
n = 3,
etc.
The normal state (the lowest possible E level)
4f
4d
4p
3d
4s
n=1
Energy
Introduction to Spectroscopes
3p
3s
2p
2s
1s
n=2
n=1
Atomic level
Molecular level
n=3
v4
v3
v2
v1
v4
v3
v2
v1
S2
T1
Absorption/Emission spectra
E.m.r. has energy determined by its frequency

E.m.r. can be absorbed and emitted by atoms/
molecules contain specific Information of A/M.
These e.m.r.s can be recorded and analysed
- the base of many spectroscopic techniques.
v4
v3
v2
v1
S0
74
Introduction to
UV-Visible Absorption Spectroscopy
The electromnetic radiations
X-Ray
UV
200nm
Visible
400nm
IR
Microwave
800nm
Wavelength (nm)
75
Introduction to UV-Visible Absorption Spectroscopy
UV Absorption Spectrometer
UV Light Source
Monochromator
90C
Detector
Monochromator
Emit fluorescent light

as energy decreases
s
p
n
p
Ground state
Energy s
Antibonding
Antibonding
ns np
Nonbonding
pp
Bonding
ss
Bonding
Electron's molecular energy levels

Sample
UV Spectrometer Applications
Protein
Amino Acids (aromatic)
Pantothenic Acid
Glucose Determination
Enzyme Activity (Hexokinase)
Visible Spectrometer Applications
Niacin
Pyridoxine
Vitamin B12
Metal Determination (Fe)
Fat-quality Determination (TBA)
Enzyme Activity (glucose oxidase)
76
Introduction to UV-Visible Absorption Spectroscopy

UV Absorption Spectra
Visible Absorption Spectra
77
Introduction to Mass Spectrometry
The working principle

1. Sample molecules are ionised in
the ion source section
2. The ions with different masses
and charges travel through a
magnet field at different speeds,
arriving to detector at different
time scales
3. The charges of ions are
converted to electricity current,
the intensity of which is then the
measure of the concentration of
the molecules
The measurement results are
directly linked to the atomic
mass of molecules
Very useful in detecting organic
molecules & in isotopic tracing
analysis
lon source
heated filament
produce electrons
beam which
collide and ionise
sample molecules
mass analyser
Ions with different mass & echanges travel at different
speeds under the magnetic
field, reaching the detector
at different time.
detector
The charges carried
by the ions are
converted to electricy
current and detected
Schematic diagramme of a single-focusing mass

spectrometr with an electron-impact ion source
78
Introduction to Mass Spectrometry

Mass spectrum of chlorine gas
m/e ratio
Corresponding ion
35
35Cl+
37
35Cl+
70
35Cl+ - 35Cl+
72
35Cl+ - 37Cl+
74
37Cl+ - 37Cl+
79
Introduction to Chromatography
The
working principle of Chromatography

The level of Interaction (adsorption) betw.
packing material & sample A, B differs,
resulting in different speeds of travel of A &
B in a media (paper, column etc.)
v
gas or
liquid
effluent
sample (A+B)
injection
column
packing, P (stationary phase)

A
carrier
(C)
effluent
Usually sample to be analysed is

injected into a carrier (gas or liquid)
Carrier is usually inert (does not react
with packing materials)
The components in sample, being
separated after chromatography, are
analysed by TCD or mass spec.
Types
Assuming P likes A (A stay with P longer)
A
B
t = to
effluent
c
t = ti
A
B
effluent
of chromatography
t
LC - Liquid (carrier & A,B) Chromatography
GC - Gas (carrier & A,B) Chromatography
c
t = te
HPLC - High Pressure Liquid Chromatography

t
80
Introduction to Chromatography
Typical GC setup
GC chromatograph
81

Introductory Chemistry B CH4751 Lecture Notes 11-20: Dr. Erzeng Xue

Hochgeladen von

Dokumentinformationen

Originaltitel

Copyright

Verfügbare Formate

Dieses Dokument teilen

Dokument teilen oder einbetten

Freigabeoptionen

Stufen Sie dieses Dokument als nützlich ein?

Sind diese Inhalte unangemessen?

Copyright:

Verfügbare Formate

Introductory Chemistry B CH4751 Lecture Notes 11-20: Dr. Erzeng Xue

Hochgeladen von

Copyright:

Verfügbare Formate

CH4751 Lecture Notes 11-20 (Erzeng Xue)

Introductory Chemistry B CH4751

CH4751 Lecture Notes 11 (Erzeng Xue)

Chemical Reaction - Observation

CH4 + 2O2 CO2 + 2H2O

CH4 + CO2 2CO + 2H2

When carrying out these reactions we found that

at 1000K(723C), reactions (1) & (2) both proceed; but

rxn (1) can go complete (until CH4 or CO2 consumed completely)

CH4751 Lecture Notes 11 (Erzeng Xue)

Chemical Reaction Thermodynamics

Each molecule contains certain types and quantity of chemical energy

There is always energy change In a chemical reaction because of

breaking / reformation of chemical bonds

There are different energies associated with a substances & a reaction

We will learn some of these energies

How to get values / do simple calculate

How to use them as a tool to study chemical reactions

CH4751 Lecture Notes 11 (Erzeng Xue)

Chemical Reaction Thermodynamics

The heat of formation, H, (also called Enthalpy of Formation or Enthalpy)

H is an energy associated with heat

DHT0 ( vi Hi0,T )prod ( vi Hi0,T )reac

refers to standard pressure (1 atm.)

Rxn(1) CH4 + 2O2 CO2 + 2H2O

Rxn (2) CH4 + CO2 2CO + 2H2

When DH<0, a reaction releases heat reaction is exothermic, as in rxn (1)

When DH>0, a reaction requires heat reaction is endothermic, as in rxn (2)

CH4751 Lecture Notes 11 (Erzeng Xue)

Chemical Reaction Thermodynamics

The Gibbs Free Energy, G, (also called Free Energy)

is a thermodynamic function related to a reaction. It is a function of H, T & S (entropy)

is specific for each substance & is a function of H, T & S (entropy)

e.g. at 1000K: GCH4=-+30, GO2=0, GCO2=-395, GH2O=-192, GCO=-200, GH2=0

DGT0 ( viGi0,T )prod ( viGi0,T )reac

Rxn(1) CH4 + 2O2 CO2 + 2H2O

DG400 DG1000=-801 kJ/mol

Rxn (2) CH4 + CO2 2CO + 2H2

DG400=+145, DG1000=-24 kJ/mol

DGT 0 reaction at equilibrium (no further change possible-dead state)

CH4751 Lecture Notes 11 (Erzeng Xue)

Chemical Reaction Thermodynamics

CH4 + CO2 2CO + 2H2

DHT0 ( vi Hi0,T )prod ( vi Hi0,T )reac

DH400 =[1x(-393)+2x(-242)]-[1x(-77)+2x(0)]= -800 kJ/mol

DH400 =[2x(-110)+2x(0)]-[1x(-77)+1x(-393)]=+250 kJ/mol

DH1000=[2x(-111)+2x(0)]-[1x(-89)+1x(-393)]= +260 kJ/mol

CH4751 Lecture Notes 11 (Erzeng Xue)

Chemical Reaction Thermodynamics

CH4 + CO2 2CO + 2H2

DGT0 ( viGi0,T )prod ( viGi0,T )reac

DG400 =[1x(-394)+2x(-224)]-[1x(-42)+2x(0)]= -800 kJ/mol

DG400 =[2x(-146)+2x(0)]-[1x(-42)+1x(-394)]=+144 kJ/mol

CH4751 Lecture Notes 11 (Erzeng Xue)

Chemical Reaction Thermodynamics

The values of DGT and DH T

DGT0 ( viGi0,T )prod ( viGi0,T )reac

Gi0,T H i0,T - T Si0,T

in which, ST is the entropy and Cp is the heat capacity at constant pressure

CH4751 Lecture Notes 11 (Erzeng Xue)

Chemical Reaction Thermodynamics

Will a reaction proceed in the direction specified?

DGT0 ( viGi0,T )prod ( viGi0,T )reac