A Level Chemistry

UNIT 4 GENERAL PRINCIPLES OF CHEMISTRY 1 NOTES ( !!"#

$ritte% &y Mr Ser'e(%t
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I%tr)*+,ti)%
This unit includes the following.
A quantitative study of chemical kinetics. Further study of organic reaction mechanisms. Entropy and equilibrium and their role in determining the direction and extent of chemical change. In the rganic !hemistry section" carbonyl compounds" carboxylic acids and their derivatives will be studied. #nowledge from $nits % and & will be necessary for $nit '

Assessme%t
The $nit examination will be %hour '( minutes. It will carry )( marks. It will contain three sections" A" * and !. Se,ti)% A is an ob+ective test Se,ti)% - short,answer and extended answer questions. Se,ti)% C will contain data questions" requiring students to extract relevant data from the data booklet. -uality of written communication will also be assessed in either section * or !.

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.INETICS / R(tes )0 re(,ti)%

I%tr)*+,ti)%
In kinetic studies the rate of chemical reactions is investigated. .ome of the factors which can affect the rate of a reaction are/ The surface area of the reactants The concentration of the reactants The temperature at which the reaction is carried out The presence of a catalyst 0ight is important for photochemical reactions

E12erime%t(l Meth)*s 0)r F)ll)3i%' Re(,ti)%s

The rate of a reaction can be determined by following some aspect of the materials which changes as the reaction proceeds. 1hen the effect of concentration on the rate of reaction is being investigated" it is important to keep other factors" such as the temperature" constant during the process.

M(ss ,h(%'es
2ass changes that take place during a reaction can be followed by placing the reaction vessel on a balance and reading the mass at specific intervals.

4)l+me ,h(%'es
1hen a gas is given off in a reaction" that reaction can be followed by measuring the volume of gas collected at various times. To do this a reaction flask could be connected to a gas syringe.

Press+re ,h(%'es
ne useful way of following the reactions of gases if a pressure change takes place is to connect the reaction flask to a pressure meter and measuring the pressure at given intervals.

Titr(ti)%
This could be used for following the reactions of an acid or alkali. It can also be used for following reactions involving iodine 3using sodium thiosulphate4. 5ipette samples of the reaction mixture would be removed from the reaction vessel" placed in a flask and the reaction quenched. It can then be titrated to find the concentration of the reaction mixture at a particular time.

P)l(rimetry .uitable for reactions involving optically active substances. Me(s+ri%' ,)%*+,tivity .uitable for reactions producing or consuming ions.

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C)l)rimetri, me(s+reme%t
If a reactant or product is coloured the reaction can be followed by using a colorimeter. This measures changes in colour intensity. A narrow beam of light is passed through the solution being investigated.

*eam of light Filter

.olution under 5hotocell test

2eter

The filter allows an appropriate colour of light to be selected. The start and finish solutions might be tried with different filters to see which give the largest change in reading. The meter is usually calibrated to measure the amount of light absorbed by the solution.

Fi%*i%' r(te
The r(te of a chemical reaction is measured by how rapidly the ,)%,e%tr(ti)% of a substance is changing. The substance may be a reactant or a product" and the sign shows whether the substance is disappearing or being formed. The rate is the instantaneous rate of fall in concentration of a reactant" or the instantaneous rate of increase in concentration of a product.

conc. of reactant Q

R(te (t 2)i%t 5 6 'r(*ie%t )0 t(%'e%t

conc. of product

C)%,e%tr(ti)% (%* R(te

It might be thought that the rate of reaction is always directly proportional to the concentration of the reactants" but this is not the case. It is only the substances that are present in the slowest step 3the rate determining step4 of a reaction that actually affect the rate of the reaction. To provide information about how the rate depends upon the concentration of reactants or catalysts the rate equation is used.

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The R(te E7+(ti)%

The extent to which concentration determines the rate of a reaction is expressed as the rate equation. These values have to be determined by experiment6 they cannot be deduced from a chemical equation 3as equilibrium equations are4. .uppose that we were investigating the reaction6 A7* ! then we would carry out experiments to see the effect of changing concentration of A and *. .uppose we obtain the following results for A.

!oncentration of A 8moldm,9 (.% (.& (.9 (.'

.o we can write6 :ate ;A<

Initial rate 8moldm,9 s,% (.(% (.(& (.(9 (.('

The rate is said to be first order with respect to A.

If we found the following results for *.

!oncentration of * 8moldm,9 (.% (.& (.9 (.'

:ate ;*<&

Initial rate 8moldm,9 s,% (.(% (.(' (.() (.%=

The rate is said to be second order with respect to *

These values can be expressed in the same equation6 :ate ;A<;*<& or :ate > k;A<;*<& This is called the r(te e7+(ti)% ?ere 8 is called the r(te ,)%st(%t for the reaction. It is constant for all concentrations of A" and *" provided that the temperature and any other conditions not specified do not change. The rate constant and order of reaction are experimentally determined. The power to which the concentration is raised is known as the )r*er )0 re(,ti)%. The general form of the rate equation is written/ :ate > k ;A<n;*<m. The value n 7 m is the overall order of the reaction.

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U%its )0 r(te (%* 89

:ate is measured in concentration8time/ usually mol dm,9 s,%. $nits of k depend on the order of reaction/ For a :er) order reaction" rate > 86 so 8 also has units of mol dm,9 s,%. For a 0irst order reaction" rate > 8;concentration<" so 8 has units of s,%. For a second order reaction" rate > 8 ;concentration<&" so 8 has units of mol,% dm9 s,%. Although the preferred unit of time is the second" if data is provided in minutes or hours it may be best to keep to the unit specified.

Fi%*i%' )r*er )0 re(,ti)% 0r)m i%iti(l r(tes9

@ou need to know three methods of measuring orders6 %. the initial rate method &. use of rateAconcentration graphs 9. the use of concentration,time graphs plus half,life. The i%iti(l r(te is the rate at the start of an experiment" when the concentrations are easy to measure since they have not had time to change. It is often not easy to measure the initial rate" but if it is known" the order of reaction is fairly easy to find. If possible" try to compare experiments in which only one concentration changes. Then" for example/ :ate > kB ;A<m If concentration of A doubles but rate does not change" m > ( 3Cero order4. If concentration of A doubles and rate doubles" m > % 3first order4. If concentration of A doubles and rate quadruples" m > & 3second order4. [If conc. is 1.5, for 1st order rate will be 1.5; for 2nd order 1.52 i.e. 2.25] If the information is presented as a number of moles" or a volume of solution" make sure that you first divide by the total volume to obtain concentrations 3or at least check that the total volume is the same in all experiments4. ?ere is an example" which has been chosen to illustrate the use of units and the calculation of the rate constant/ The table shows the results of three experiments to establish the orders of reaction with respect to components A and *. Find these orders" and calculate the rate constant for the reaction. !oncentrations are all %.( mol dmA9.

Experiment 5 :

Dolume of A8cm9 %(( &(( 9((

Dolume of *8 cm9 &(( &(( '((

Dolume of water8 cm9 F(( =(( 9((

:ate8%(AE mol dmA9sA% &.& '.' &=.=

The water is added to make up the volume to a suitable total" in this case %(((cm 9 in each case.

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m % !alculation/ assume r(te 6 8 ;A< ;-< !omparing 5 and -/ concentration of A doubles" and rate also doubles. Therefore reaction is 0irst )r*er in A 3m > %4.

Gote that we cannot find a direct comparison in which only * changes. 1e must allow for the effect of changing A first. !omparing 5 and :/ concentration of A increases by a factor of three" so this alone would change the rate to 9 H &.& > =.=. In addition the concentration of * doubles" and rate goes up by a further factor of ' 3i.e. from =.= to &=.=4. Therefore" reaction is se,)%* )r*er i% -" 3since rate ;&<n" n>& 4.

To find the rate constant we can substitute in the rate expression for any of the experiments. Gote the heading for :ate in the table/ all the figures have been divided by%(AE mol dmA9sA%" so the AE rate for 5 is &.& H %( mol dmA9sA%/ rate > k ;A<m;*<n Expt. 5/ &.& H %(AE mol dmA9sA% > k k >
2.2 10 5

> k ;A<;*<&
[100 1.0 1000 ] [ 200 1.0 1000 ]
2

mol9 dmA)

0.1 0.04

3 mol =5.5 10

A&

dm=sA%

R(te/C)%,e%tr(ti)% 'r(2hs=
If the rate can be measured at different concentrations 3e.g. by the initial rate method4" a Cero order reaction will show no change 3horiContal line4" while a first order reaction will increase linearly. For a second order reaction" rate ;conc<&" so a graph of rate against ;conc<& would be a straight line.
first order

rate o reaction

rate o reaction

second order

zero order

concentration

concentration

C)%,e%tr(ti)%/time 'r(2hs (%* h(l0 li0e9

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The h(l0 li0e of a reactant which is not in excess is the time taken for its concentration to decrease to half its initial value. For a 0irst )r*er reaction" the half,life is always constant/
100 " o reactant remainin#

50

first order

25 12.5 10 20 30 time/min

?ere it takes %( min for the % of reactant remaining to fall from %(( to E(" and another %( min to fall from E( to &E 3or from I& to '%" etc4. For a second order reaction successive half,lives double. Gote that if the graph of concentration against time is str(i'ht" order is :er). If it is curved 3as above" or falling more steeply at first4 you need to check successive half lives to find if they are constant 3order %4 or if they double 3order &4.

E1(m2les )0 ,)%,e%tr(ti)%>r(te st+*ies

ne method of determining rate is to follow the reaction over a period of time. *romine and methanoic acid react as follows/ *r&3aq4 7 ?! &?3aq4 &?*r3aq4 7 !

&3g4

The reaction can be followed by calorimeter" measuring the colour intensity of the bromine. A calibration plot of calorimeter readings for known concentrations would be made so that it is possible to convert calorimeter readings to bromine concentration. In this experiment the effect of changing the bromine concentration" a high concentration of methanoic acid is used" so that its concentration changes very little as the concentration of the bromine changes significantly.

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:eadings for such an experiment are shown below6

Time 8s ( 9( =( )( %&( %I( &'( 9=( 'I( =((

;*romine< 8moldm,9 (.(%(( (.(()( (.((I% (.((F9 (.((F9 (.((E9 (.(('' (.((&I (.((&( (.((%9

5lot a graph of bromine concentration against time. Jraw tangents at intervals to fill in the table below and find the rate of change of the bromine concentration at these times.

Time 8s E( %(( %E( &(( &E( 9(( '(( E((

;*r&< 8moldm,9 (.((I= (.((F% (.((=( (.((E( (.(('& (.((9E (.((&E (.((%I

:ate of reaction 8moldm,9s,% &.)& x %(,E &.'( x %(,E &.(' x %(,E %.F( x %(,E %.'E x %(,E %.%) x %(,E (.I% x %(,E (.=E x %(,E

5lot a new graph of the rate values obtained against the bromine concentration. This graph produces a straight line showing the reaction to be first order with respect to bromine concentration.

Another method of determining rate is to measure the initial rate 3before any significant concentrations changes have occurred4 using different starting concentrations. ?ydrogen reacts with nitrogen3II4 oxide at I((o! as follows/ &?&3g4 7 &G 3g4 &?& 3g4 7 G&3g4 :esults of an initial rate investigation of this reaction are shown below.

Experiment % & 9 ' E =

Initial ;G < 8 moldm,9 = x %(,9 = x %(,9 = x %(,9 % x %(,9 & x %(,9 9 x %(,9

Initial ;?&< 8 moldm,9 % x %(,9 & x %(,9 9 x %(,9 = x %(,9 = x %(,9 = x %(,9

Initial rate of reaction 8 moldm,9 s,9 9.( x %(,9 =.( x %(,9 ).( x %(,9 (.E x %(,9 &.( x %(,9 '.E x %(,9
-$

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!omparing experiments %" & and 9" it can be seen that as the concentration of hydrogen increases" the rate of reaction increases proportionately. This shows that the reaction is first order with respect to the hydrogen. !omparing experiments '" E and =" it can be seen that as the concentration of nitrogen3II4 oxide increases" the rate of reaction increases by the square of the concentration increase.

Experiment ' E =

Initial ;G < 8 moldm,9 % x %(,9 & x %(,9 9 x %(,9

!hange in ;G < Expt ' x & Expt ' x 9

Initial rate of reaction 8 moldm,9 s,9 (.E x %(,9 &.( x %(,9 '.E x %(,9

!hange in rate Expt ' x ' Expt ' x )

This shows that the reaction is second order with respect to the nitrogen3II4 oxide. .o the rate equation is :ate > k;?&<;G <&

*y substituting in values the value of k can be determined. $sing experiment 9 ).( x %(,9 > k x 9 x %(,9 x 3= x %(,94& k> $nits of k >

$.0 % 10-3 3 % 10-3 % &6 % 10-3'2 mo(dm-3 s-3 mo(dm-3 s-3 % &mo(dm-3 s-3'2

> I.99 x %(,' > mol,&dm=s,%

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Re(,ti)% Me,h(%isms
2any reactions actually take place in a number of steps. The way in which atoms" ions or molecules interact" stage by stage" is known as the reaction mechanism. :ate studies can provide useful information about the reaction mechanism. In a reaction which has several stages" the different stages will proceed at different rates. It is the slowest step which will determine how long the reaction takes. This step is called the rate determining step. .ince the rate determining step controls how long the reaction takes" then the substances in this step will appear in the rate equation. The rate equation then provides evidence about the substances involved in the rate determining step. The reaction between propanone and bromine is a first order reaction overall. :ate > k ;propanone<%;bromine<( The rate then is proportional to the concentration of propanone" but independent of the concentration of bromine. This suggests that the reaction takes place in a number of stages" and that only the propanone is involved in the rate determining step. e.g. For an .G% reaction two steps are involved R? R@ @ ?> step % slow @ R @ OH> ROH step & fast The rate depends on the slow step %. r(te 6 8;R?< 0irst )r*er

For an .G& reaction there is a rate determining slow step involving two species. R? @ OH> HO>>RA? slow r(te 6 8;R?<;OH>< se,)%* )r*er

Me,h(%isms (%* .i%eti, *(t(

!hemical reactions occur when molecules 3or atoms" or free radicals" or ions4 collide/ at a given temperature a constant proportion of collisions is likely to be successful. If molecules of A and * are in the same vessel" the number of collisions between A and * depends on their concentrations/ number of AA* collisions ;A< ;*< i.e. if we double the number of A molecules in the vessel we will get twice as many AA* collisions6 if we double both A and *" there will be four times as many collisions. If A and * take part in a simple" one,step reaction" the rate of reaction will depend on the number of AA* collisions/ rate of reaction ;A< ;*< In general" in a one,step reaction" the rate of reaction is proportional to the product of the concentrations of each species colliding. The number of species 3atoms" molecules or ions4 which collide in a one,step reaction is called its m)le,+l(rity= e.g. A products6 rate ;A<6 unimolecular & A 7 A products rate ;A< bimolecular A 7 * products rate ;A<;*< bimolecular A 7 * 7 2 products rate ;A<;*<;2< trimolecular Trimolecular reactions are extremely unusual.
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The mechanism for a reaction can be proposed with help from kinetic data but some speculation is needed. %. The rate equation gives us information about what reacts in the rate determining step. &. .ensible products must be suggested for the rate determining step. 9. If more molecules of reactant remain and more product molecules are still to be formed more steps must be proposed. 1rite rate equations for the following verall equation/ .teps &A 7 * ! J ! L 0 L .low Fast 3catalysed by acid4 .low Fast !&?E ? 7 *r , ;!&?E,*r, ?,< !&?E ? 7 *r , .low Fast

&A * 7 J

verall equation/ .teps

E 7 K K 7 ?7 0 7 E

?, ?,

verall equation/ .teps

!&?E*r 7 !&?E*r 7

;!&?E,*r, ?,<

verall equation .teps

3!?949!*r 7 3!?949!*r 3!?949!7 7

?,

3!?949! ? 7 *r , 3!?949!7 7 *r , 3!?949! ? .low Fast

?,

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The Tr(%siti)% St(te The)ry

The transition state theory says that when molecules collide and react" they move through a state of instability or high potential energy. This state of high potential energy is called the transition state or the activated complex. The energy required to attain the transition state is the activation energy.

-ransition state )*

)ner#+

,eaction coordinate
An example of this is the hydrolysis of a primary halogenoalkane. :,M 7 ?, ;? ,:,M<, : ? 7 M, Transition state In some reactions an intermediate is formed. For example in the hydrolysis of a tertiary halogenoalkane" a carbocation is formed. :,M :7 7 M, 7 The : carbocation is a reactive intermediate. This then reacts with the ?, to produce the alcohol. 1hen a reactive intermediate is formed the reaction goes through two transition states.

-ransition state 1

-ransition state 2

)ner#+

,eactive intermediate

,eaction coordinate
The higher the value of the activation energy" the lower the number of effective collisions and so the lower the rate constant.

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:ate and :eaction 2echanism in :eal .ystems

:esults from kinetics studies provide information about reaction mechanism. The rate equations for the hydrolysis of primary and tertiary halogenoalkanes are different. For hydrolysis of primary halogenoalkanes the rate equation is/ For hydrolysis of tertiary halogenoalkanes the rate equation is/ :ate > k;:M<; ?,< :ate > k;:M<

The different rate equations arise because the hydrolysis of primary halogenoalkanes takes place by a different mechanism than that for tertiary halogenoalkanes. The reaction mechanism for the hydrolysis of primary halogenoalkanes is as follows/

/ /

/ . 0 /1

/ / . /

/1

The rate determining step in which the :,M bond breaks involves the halogenoalkane and the hydroxide ion. ?ence both these feature in the rate equation. It is designated .G& because there are two species involved in the :J..

Transition state

The reaction mechanism for the hydrolysis of primary halogenoalkanes is as follows/

The stability of a tertiary carbocation means that the breaking of the :,M bond can occur without the necessity of the hydroxide ion. ?ence only the :M features in the rate equation. It is designated .G% because there is only species involved in the :J..

, ,

, . 0

, , . ,
!arbocation intermediate

/1

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Iodine reacts with propanone as follows I& 7 !?9! !?9 !?&I! !?9 7 ?I This reaction is catalysed by the presence of an acid. The rate equation for this reaction is :ate > k;!?9! !?9<;?7<

This tells us that the rate determining step for this reaction involves only the propanone and the hydrogen ions.

/ / . /

. 1

/ . /+ /

/ / . /

+
. 1 /

/ . / /

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Tem2er(t+re (%* r(te

ften an increase in temperature of %(o! can double the rate of reaction. In terms of absolute temperature this means a change of temperature from 9)E # to '(E #6 so the proportional change in rate vastly outweighs the proportional change in temperature. This cannot be explained in terms of speed of particles" as their speed is determined by the absolute temperature. In topic &.I" it was seen that activation energy is an important factor for rate of reaction when the temperature is altered. The activation energy was connected with the *oltCmann distribution of energy.

)* )*

At a higher temperature the proportion of particles with an energy equal to" or greater than" the activation energy increases significantly.

-1

-2

-3 -32-22-1

-1

-2

-3 -32-22-1

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The Arrhe%i+s E7+(ti)%

An important equation linking activation energy" temperature and rate of reaction is the Arrhenius equation.

3 4 *e
In this equation" and

-)*/,-

k is the rate of reaction" EA the activation energy" : the gas constant T the temperature in #elvin. A is the Arrhenius constant connected with the number of collisions and collision orientation.

It can be seen from this equation that as the activation energy increases" the rate constant will decrease and that as the temperature increases the rate constant also increases. The table below shows how the rate constant might change with activation energy.

Activation energy 8 kLmol,% '( E( =( F(

:ate constant F'I(( %9%9 &9.( (.'('

The table below shows how the rate constant might change with temperature. This is based on the kinetics for the reaction/

&?I Temperature 8# &F9 'F9 =F9 FF9 IF9 Taking log to base e in

? & 7 I& :ate constant 9.99 x %(,&= &.%& x %(,%( E.'E x %(,' '.)) x %(,& %.=&

3 4 *e

-)*/,-)*/,-

ln k > ln A 7 ln e

ln k > ln A A EA8:T

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This can be used to find a value of the Activation Energy. A graph of y > a A bx" appears as follows

+ 7ntercept 4 a

5radient 4 6

%
The log version of the Arrhenius equation can be plotted in a similar way

y > a A bx ln k > ln A A EA8: 3%8T4

1hen a graph of ln k is plotted against %8T" the slope of the line is AEA8:

(n 3 4 (n *

5radient 4 )*/,

1/If k is calculated for different values of T then a plot of ln k against %8T gives a line of gradient > , Ea8:. If k is calculated for different values of T then a plot of l)' 8 against %8T gives a line of 'r(*ie%t 6 > E(B 9CR9

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Determi%(ti)% )0 the A,tiv(ti)% E%er'y 0)r ( re(,ti)%

.odium thiosulphate reacts with dilute hydrochloric acid according to the equation/

.&

&, 9 3aq4

7 &?73aq4

&3g4

7 .3s4 7 ?&

3l4

The sulphur forms a suspension and the mixture becomes progressively more cloudy. The acid and the thiosulphate are mixed at a particular temperature and the time taken for the sulphur formed to obscure a mark behind the tube is noted.

:ar3 on side o 6ea3er 8ater 6ath ,eaction mi%t9re

The reaction is then carried out at different temperatures. :esults are shown below.

Temperature Temperature Time 8 s %8T %8time ln %8time 8o! 3T4 8# 8 #,% 8 s,% 3rate4 =( 999 %& (.((9((9 (.(I9999 ,&.'I')% E& 9&E %I.= (.((9(FF (.(E9F=9 ,&.)&9%= ''.E 9%F.E &I (.((9%E( (.(9EF%' ,9.99&& '( 9%9 9= (.((9%)E (.(&FFFI ,9.EI9E& 9'.E 9(F.E E( (.((9&E& (.(&(((( ,9.)%&(& &I 9(% F' (.((99&& (.(%9E%' ,'.9('(F &% &)' %%= (.((9'(% (.((I=&% ,'.FE9E)
5lot a graph of ln k against %8T. Find the gradient $se the relationship" Kradient > ,EA8: to calculate the activation energy for the reaction given that : > I.9 L#,%mol,%.

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C(t(lysts (%* r(te

In $nit &" it was seen that catalysts work by providing an alternative path for the reaction at a lower activation energy.

The effect of this can be shown diagrammatically in a 2axwell,*oltmann distribution curve.

)* ;ncata(+sed reaction

)* .ata(+sed reaction

The effect of lowering the activation energy even by proportionally small amounts is illustrated in the table in the NArrhenius EquationO section. 2any catalysts alter the activation energy considerably.

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E%tr)2y
E1)thermi, (%* E%*)thermi, Re(,ti)%s
2ost chemical reactions give out heat energy as they take place" so the products have less energy 3and so are more stable4 than the reactants. These are e1)thermi, reactions. 1hen ethanoic acid is added to sodium hydrogencarbonate" a reaction takes place and the temperature decreases" so heat energy is being taken in. This is an example of an endothermic reaction in which the products have more energy 3are energetically less stable4 than the reactants. An endothermic reaction can be compared to a ball spontaneously rolling uphill or a pencil lying down springing upright.

1hat enables chemical reactions to do what is energetically unfavourableP Energy considerations by themselves are clearly not sufficient to explain why chemical reactions take place. The other factor that is important for chemical reactions is e%tr)2y. Essentially materials go to their most likely condition6 the most probable situation , that is where there is the maximum freedom. The greater the freedom molecules have" the greater the entropy. As molecules become more randomly distributed their entropy increases. 1hen molecules gain energy they gain freedom of movement and so their entropy increases. The symbol used for entropy is .. .olids have restricted movement for the molecules in them" so they have lower entropies than other states. 5erfect crystals at ( #elvin have Cero entropy. In liquids" the molecules have greater freedom of movement than solids" so liquids have higher entropies than solids. This means that dissolved substances will have higher entropies than the solid. The molecules in gases have much greater freedom of movement and so have comparatively high entropy values. !omplex molecules generally have higher entropies than simple molecules as there are more ways they can arrange themselves.

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The table below gives entropy values of selected substances at &)I#. S+&st(%,e St(te E%tr)2y BE.>1m)l>1 Aluminium .olid &I.9 .ilicon dioxide .olid '%.I 1ater 0iquid F(.( Argon Kas %E'.F !arbon dioxide Kas &%9.= It can be seen from this table that the more ordered the state" the lower the value of entropy. The solids have the lowest values. 0iquids have higher values and gases have still higher values. The table below gives entropy values of certain alkanes. Al8(%e St(te E%tr)2y BE.>1m)l>1 2ethane Kas %I=.& Ethane Kas &&).E 5ropane Kas &=).) *utane Kas 9%(.% 5entane 0iquid &=%.% The table of alkanes shows that as the complexity of the gaseous molecules increases so do the entropy values. 5entane has a lower value than butane because it is liquid rather than gas. 1hen a chemical reaction takes place new substances are formed. The products of a reaction will have different entropy values to the reactants" so the entropy of Nthe systemO changes. The change in entropy can be found using the following equation/

FSSYSTEM 6 FSPRODUCTS > FSREACTANTS

For spontaneous change to take place the entropy must increase. !hanges that incur an increase in entropy include/ Formation of gas molecules Jissolving of a solid Jecomposition of a substance 3as the resulting components have greater freedom of movement4 Kases becoming more randomly distributed 3diffusion4 1hen magnesium burns the magnesium atoms combine with oxygen molecules to form a magnesium oxide ionic lattice. &2g3s4 7 &3g4 &2g 3s4 In this change a gas is converted to a solid" so the entropy in this change seems to decrease and break our rule about spontaneous change. Indeed" the entropy change is ,&&%.EL#,%mol,%. ?owever as the reaction takes place energy is given out and so the surrounding molecules gain energy and so gain entropy.

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1hen considering entropy in changes" it is necessary to consider what happens to the surroundings as well as the system 3chemical reaction4 itself.

FSTOTAL 6 FSSYSTEM @ FSSURROUNDINGS

Any entropy increase in the surroundings comes from the energy which the system gives out. The increase in entropy depends upon the proportional increase in energy of particles in the surroundings. If for example the surroundings gain &(kL of energy" the proportional increase is greater if the surroundings originally have low energy. Temperature is a measure of the energy of molecules" so the change in entropy in the surroundings is6 FSSURROUNDINGS >

It can be seen from this that as the temperature becomes higher" the value of Q..$:: decreases.

-</ -

$GJIGK.

A reaction is feasible if is Q.T TA0 positive. This will depend upon the change in entropy of the system and the change in entropy of the surroundings. FSTOTAL 6 > FHBT @ FSSYSTEM The table below shows the various possibilities.

Q..@.TE2 @ > > @ @ >

Q..$:: @ @ @ > > >

$GJIGK.

!omparative values Q..@.TE2 R Q..$:: Q..@.TE2 S Q..$:: Q..@.TE2 R Q..$:: Q..@.TE2 S Q..$::

Q.T @ > @ @ > >

TA0

$GJIGK. $GJIGK. $GJIGK. $GJIGK.

Feasibility of reaction @es Go @es @es Go Go

For the example of burning magnesium Q? > ,%&('kLmol,% at &)I#. .o Q..$:: $sing Q.T
$GJIGK.

> ,3,%&('48&)I > 7'.('(9kL#,%mol,%

$GJIGK.

TA0

> Q..@.TE2 7 Q..$::

!onverting 7'.('(9kL#,%mol,% to 7'"('(.9 L#,%mol,% Q.T

TA0

> 3,&&%.%4 7 37'"('(.94 > 9"I%I.I L#,%mol,%

=otice that the 9nits o > are in ?@-1mo(-1. 7n partic9(ar ? not 3?

It can now be seen that the overall entropy change is positive" showing that the reaction is feasible.

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Other e1(m2les !ombustion of carbon

!3s4 7
Q..$::

&3g4

&3g4

<>>A>-): </

B3.02 ?@-1mo(-1 -3$3.5 3?mo(-1

$GJIGK.

> ,3,9)9.E48&)I > 7%.9&('F kL#,%mol,% 3or 7%"9&(.'F L#,%mol,%4 > Q..@.TE2 7 Q..$::
$GJIGK.

$sing Q.T

TA0

=otice that the 9nits o > are in ?@-1mo(-1. 7n partic9(ar ? not 3?

Q.T TA0 > 379.(&4 7 37%"9&(.'F4 > 7%"9&9.') L#,%mol,% The positive value shows that this reaction is feasible.

Jecomposition of calcium carbonate !a! 93s4 !a 3s4 7 ! Q..$::

$GJIGK.

&3g4

<>>A>-): </

B165 ?@-1mo(-1 B17! 3?mo(-1

> ,37%FI48&)I > ,(.E)F kL#,%mol,% 3or ,E)F L#,%mol,%4 > Q..@.TE2 7 Q..$::
$GJIGK.

$sing Q.T

TA0

Q.T TA0 > 37%=E4 7 3,E)F4 > ,'9& L#,%mol,% The negative value shows that this reaction is not feasible at room temperature.

.olutions
1hen an ionic substance is placed in water" the water molecules" being highly polar" are attracted to the ions. The oxygen in the water molecule carries a partial negative charge and is attracted to cations. The hydrogen in the water molecule carries a partial positive charge and is attracted to anions. The process of water molecules linking to ions is called hydration of ions. The water molecules are vibrating" so as they bond to the ions they shake the ions free from the lattice. The process of dissolving is shown below.

+ +

+ + -

+ +

+ + -

+ +

+ + -

+ + - + + -

.ome ionic compounds do not dissolve in water because the electrostatic attraction between the ions is too great for the water molecules to overcome. There are two key energy processes taking place as an ionic substance dissolves. The lattice has to be broken apart. This is an endothermic process. As new bonds form between the water
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molecules and the ions an exothermic process takes place. The energy change that takes place when a solution dissolves is a balance of these two energy changes. This is illustrated in the diagram below.

5aseo9s ions )ntha(p+ Cattice entha(p+ 7onic so(id )ntha(p+ o >o(9tion /+drated ions

:B&#' B 0-&#' </Cat /+dration entha(p+ :0&s' </>o(n :B&aD' B 0-&aD'

<//+d

Jefinitions for Enthalpy !hange in .olution 0attice Enthalpy"

The heat energy given out 3exothermic enthalpy change4" when one mole of a crystal lattice is formed from separate" gaseous ions at an infinite distance apart under standard conditions. For one mole

:B&#' B 0-&#'

:0&s'

Enthalpy of ?ydration"
The heat energy given out when one mole of gaseous ions dissolve in an excess of water to form an infinitely dilute solution under standard conditions. For one mole

:B&#' B aD 0-&#' B aD

:B&aD' 0-&aD'

Enthalpy of .olution"
The solution enthalpy is a measure of the amount of heat energy change when one mole of substance is dissolved in excess water.

:B&#' B 0-&#' B aD

:B&aD' B 0-&aD'

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0attice Enthalpy
The lattice enthalpy is a measure of the strength of an ionic lattice. .ome values of lattice enthalpy are given below.

C)m2)+%* GaF Ga!l Ga*r GaI #!l :b!l !s!l 2g!l& !a!l& 2g !a

L(tti,e e%er'yB 8Em)l>1 ,)&9 ,FF= ,F'& ,=)) ,F(% ,=FE ,='E ,&')9 ,&&9F ,9)99 ,9E%9

It can be seen that as the siCe of the anion increases" the value of the lattice energy drops. This is because the sum of the radii increases 3distance between the centres of charge increases4" and so electrostatic attraction decreases as and the lattice enthalpy decreases a consequence. Increasing siCe of cation also causes a decrease in the lattice enthalpy. The higher the charge on either or both of the ions" the greater the lattice enthalpy. As the charge on the ion increases the electrostatic attraction also increases" so the lattice energy becomes greater.

?ydration Enthalpy
The hydration enthalpy is a measure of the attraction between an ion and water molecules. .ome values of hydration enthalpy are given below.

I)% 0i7 Ga7 #7 2g&7 !a&7 Al97

Hy*r(ti)% e%th(l2yB 8Em)l>1 ,')) ,9)( ,9(E ,%I)% ,%E=& ,'=%9

I)% F, !l, *r, I,

Hy*r(ti)% e%th(l2yB 8Em)l>1 ,'EF ,9I% ,9E% ,9(F

It can be seen that as the siCe of the cation increases" the value of the hydration enthalpy drops. This is because the distance between the centre of ionic charge and the water molecule increases" and so electrostatic attraction decreases as and the hydration enthalpy decreases a consequence. Increasing siCe of anion also causes a decrease in the hydration enthalpy fro similar reasons. The higher the charge on the ion" the greater the hydration enthalpy. As the charge on the ion increases the electrostatic attraction also increases" so the hydration enthalpy becomes greater.

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Enthalpy of .olution
The enthalpy of solution is related to the lattice and hydration enthalpies as follows/ Q?soln > , Q?latt 7 Q?hyd !onsidering sodium chloride

=aB&#' B .(-&#' </Cat )ntha(p+ =a.(&s' <//+d =aB&aD' B .(-&aD' </>o(n

Q?soln > , Q?latt 7 Q?hyd Q?soln3Ga!l4 > , 3,FF=4 7 3,9)( 7 ,9I%4 > 7EkLmol,%
It can be seen that the enthalpy of solution for sodium chloride is endothermic. To understand why the process of dissolving occurs spontaneously it is necessary to look at the entropy changes involved in the process. Q.T TA0 > Q..@.TE2 7 Q..$:: $GJIGK. Although this is an endothermic reaction making Q..$:: $GJIGK. negative" the Q..@.TE2 has a high positive value because the process of dissolving means that a highly ordered ionic lattice becomes a much less ordered solution of ions. The dissolving of ammonium chloride is even more endothermic with a Q?soln of 7%= kLmol,%.

=/4B &#' B .(-&#' </Cat )ntha(p+ =/4B &aD' B .(- &aD' <//+d

</>o(n 4 B16 3?mo(-1 =/4.(&s'

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The values of system entropy and enthalpy of solution are shown below.

<>>A>-): </so(n
.o Q..$:: !alculating Q.T Q.T Q.T
TA0 $GJIGK.

B27!.5 ?@-1mo(-1 B16 3?mo(-1

> ,37%=48&)I > ,(.(E9F kL#,%mol,% 3or ,E9.F L#,%mol,%4

TA0

.
$GJIGK.

> Q..@.TE2 7 Q..$::

TA0

> 37&FI.E4 7 3,E9.F4 > 7&&'.I L#,%mol,%

TA0

The positive value of Q.T

allows us to predict that ammonium chloride will be soluble.

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E7+ili&ri+m
Dy%(mi, E7+ili&ri+m
Equilibrium involves reactions which do not go to completion. These reactions are reversible. If we consider a reaction between A and * to form ! and J which is reversible. 1hen A and * are mixed" the molecules will form ! and J. ?owever" as soon as molecules of ! and J are formed and collide they can also react to become A and *. .uch a reaction is written6 A 7 * ! 7 J The reaction reaches a point at which the proportion of each chemical becomes constant. This is described as equilibrium.

Equilibrium is when a reaction has a constant concentration of reactants and products.

The forward and backward reactions continue" but in balance" the same number of molecules reacting in each direction" so a dynamic equilibrium exists.

Jynamic equilibrium is when a reaction has a constant concentration of reactants and products exist as the forward and backward reactions takes place in both directions at equal rates.

5+(%tit(tive E7+ili&ri(
In this section we deal with the quantitative aspects of equilibria. -uantities of materials involved in equilibrium reactions can be expressed as a concentration in moles per dm9" or for gases as a partial pressure. In a vessel containing a mixture of gases" the 2(rti(l 2ress+re of one gas is the pressure it would exert if it occupied the vessel alone. The total pressure in a mixture of gases is the sum of all the partial pressures. It follows that/ 2(rti(l 2ress+re )0 A 6 m)le 0r(,ti)% )0 A G t)t(l 2ress+re For example" if one gas makes up %ET by volume of the mixture 3or %ET of the molecules4 its partial pressure will be (.%E H 5" where 5 is the total pressure. The m)le 0r(,ti)% of a gas in a mixture is the fraction of the total number of moles of gas present/ m)le 0r(,ti)% )0 A 6
no. o mo(es o * tota( no. o mo(es

The sum of all the mole fractions must always be %.(. If nitrogen and hydrogen are mixed in a %/9 molar ratio" and together they have a partial pressure of I(( 25a" then/ partial pressure of nitrogen > U H I(( partial pressure of hydrogen > V H I(( > &(( 25a > =(( 25a.

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- 2$

E1(m2les & moles of nitrogen" 9 moles of oxygen and %mole of carbon dioxide were placed in a vessel. The total pressure was E atmospheres. !alculate the partial pressure of each of the gases in the mixture.

Total moles > & 7 9 7 % > = 5G& > & 8 = x E > %.=Fatm 5 & > 9 8 = x E > &.Eatm 5! & > % 8 = x E > (.I9atm
&.Ig of carbon monoxide" I.Ig of carbon dioxide and &.9g of nitrogen dioxide were placed in a vessel. The total pressure was Iatm. !alculate the partial pressure of each of the gases in the mixture.

2oles ! > &.I 8 &I > (.% mol" 2oles ! & > I.I 8 '' > (.& mol" 2oles G & > &.9 8 '= > (.(E mol" Total moles > (.% 7 (.& 7 (.(E > (.9Emol 5! > (.% 8 (.9E x I > &.&)atm 5! & > (.& 8 (.9E x I > '.EFatm 5G & > (.(E 8 (.9E x I > %.%'atm

E7+ili&ri+m e12ressi)%
0e !hatelier will give us an idea of the direction of change" but" where concentrations are involved" we can calculate precisely what happens. In general" for a reversible reaction between ( moles of substance A" and & moles of substance * etc/ (A 7 &* ,! 7 *J when the system has come to equilibrium" the ratio given by #c will be constant/ #c >
[.] c a [ F] [ E] d 6 [*]

where ;!< means concentration at equilibrium" normally in mol dmA9

i.e. equilibrium constant > 3product of products4 divided by 3product of reactants4. The main mistakes students make over this are to forget that the right hand side of the equation goes on to " and to forget that concentrations are multiplied together" not added. #c is called the ,)%,e%tr(ti)% e7+ili&ri+m ,)%st(%t. For gases" it is often more convenient to express this constant in terms of partial pressures/ #p >
c d G G . F a 6 G* GE

where G. is the partial pressure of ! at equilibrium

#p is called the 2ress+re e7+ili&ri+m ,)%st(%t9 Gote that the both types of equilibrium constant will have units" unless 3c 7 d4 > 3a 7 b4. They therefore normally have different numerical values" for the same position of equilibrium. The equilibrium constant is only affected by temperature/ it does not change if concentrations or pressures are varied" nor in the presence of catalysts. The osition of equilibrium" however" is normally affected by changes in concentration.
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A large !alue for #c or #p usually means there is a high concentration of products 3on top in the equations4 at equilibrium " and so the theoretical yield is high. !onversely" a small !alue for #c or #p usually means there is a very low theoretical yield possible" when the reaction has come to equilibrium.

U%its )0 the E7+ili&ri+m ,)%st(%t9

The units of the equilibrium constant depend upon the equilibrium expression and must be calculated by substituting in the units of concentration or pressure and cancelling down. E1(m2les 1rite #c expressions for the following and give the units &Fe973aq4 7 &I,3aq4 &Fe&73aq4 7 I&3aq4

@c 4
G?93aq4 7 ?&
3l4

[He2B]2 [72] [He3B]2 [7-]2 [=/4] [1/-] 4 [=/3] [/21]

dm3mo(-1 =o 9nits

G?'3aq4 7

?,3aq4

@c
!u&73aq4 7 'G?93aq4 !u3G?94'&73aq4

@c
!?9!
&

[.9&=/3'42B] 4 [.92B] [=/3] 4

dm12mo(-4

?3aq4 7 !&?E ?3aq4

!?9!

&

!&?E3aq4

7 ?&

3l4

@c

[./3.12.2/5] [/21] 4 [./3.12/] [.2/51/]

=o 9nits

1rite #p values for the following and give units 3based on pressure given in atm4 G&3g4 7 9?&3g4 &G?93g4 G 2

@p 4
&.
&3g4

=/3 3 /2 =2

*tm-2

&3g4

&.

93g4

G>132 @p 4 G>12 G12

2

*tm-1

1hen a reaction contains materials which are all gases or aqueous solutions" the equilibrium is said to be homogeneous. If a reaction contains solid or liquid components" the equilibrium is said to be heterogeneous" and the expressions do not include these components. !a!
93s4

!a

3s4

7 !

&3g4

@p 4 G.12
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*tm
- 31

9Fe3s4 7 '?&

3g4

Fe9

'3s4

7 '?&3g4

G/24 @p 4 G/214

=o 9nits

5b!l&3s4

5b&73aq4

7 &!l,3aq4

@p 4

[G62B] [.(-]2

:o(3dm-$

E7+ili&ri+m C(l,+l(ti)%s9
1e will normally find values for #c and #p from experimental data. "#am le 1$ %alculate &c for the esterification of ethanoic acid b' ethanol gi!en that for a 1dm( of this homogeneous liquid equilibrium the amounts resent are as shown below. CHCCO H @ C HHOH CHCCO C HH @ H O Equilibrium amount8mol (.(&EE #c > ;!?9!
&

(.(&'E
&

(.(EI'

(.('EF

!&?E< ;?& < 8 ;!?9!

?< ;!&?E ?<

#c > (.(EI' x (.('9F8 (.(&EE x (.(&'E > '.% 3no units for esterification reaction4 "#am le 2; In the reaction gi!en below, ).1 mol of * is mi#ed with ).( mol of +, dissol!ed in ).5 dm( of water, and allowed to come to equilibrium, when the amount of , is found to be ).)- mol. .ind the equilibrium constant, &c. A 7 &* ! 7 9J At start/ (.% (.9 ( ( At equilibrium" we know/ therefore/ (.%,(.(& (.9,(.(' (.(& (.(=

3since % A 9 J" (.(& A (.(= J6 (.(' * (.(= J " and (.(&! is formed4. #c >
[.] [ F] [*] [ E]
3

>

&0.02/0.5' &0.06/0.5' &0.0!/0.5' &0.26/0.5'

3 2

> 0.04 0.00172!

0.16 0.2704

> %.=(H%(A9 mol dmA9

Gote that the number of moles is divided by the total volume 3(.E4 to obtain the concentration. "#am le 2$ If at 55o% the artial ressure of nitrogen dio#ide in an equilibrium mi#ture is ).-/atm and the artial ressure of dinitrogen tetrao#ide in the mi#ture is ).((atm what is the !alue of & for the reaction at this tem erature0 N O4('# NO ('# #p > p&G &3g48 pG& '3g4 #p > (.=Fatm&8(.99atm #p > %.9=atm
- 32

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"#am le ($ In the dissociation of hos horus entachloride, at 11)2% and 2.)) atm ressure, the hos horus entachloride is found to be 3)% dissociated. .ind & . !onsider % mole of reactant. 5!lE3g4 At start %.(( At equilibrium (.=( mole fractions
0.6 1.40 0.6 H& 1.40

5!l93g4 (.(( (.'(

0.4 1.40

!l&3g4 (.(( (.'(

0.4 1.40

W total %.'( mol

partial pressures

0.4 H& 1.40

0.4 H& 1.40

(.IEFatm

(.EF%atm

(.EF%atm

#p >

GG.(3 G.(2 GG.(5

>

0.571 0.571 > (.9I( atm 0.!57

The e00e,t )0 tem2er(t+re )% ., (%* .29

#c" #p and the position of equilibrium are affected by temperature in endothermic and exothermic equilibria. The effects are the same as predicted by 0e !hateliers principle. E1)thermi, re(,ti)%s/ Temperature rise/, position of equilibrium moves to left" #p and #c become smaller. Temperature fall/, position of equilibrium moves to right" #p and #c become bigger E%*)thermi, re(,ti)%s/ Temperature rise/, position of equilibrium moves to right" #p and #c become bigger. Temperature fall/, position of equilibrium moves to left" #p and #c become smaller.

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E7+ili&ri+m (%* E%tr)2y

Equilibrium is linked to entropy. For a reaction to be feasible the total entropy change 3the sum of change in system entropy and change in surroundings entropy4 must be positive. The higher the positive total entropy change" the further an equilibrium is driven in that direction and the greater the equilibrium constant. The link is given by the following equation/ FS 6 R l% . ?ere Q. is the change in total entropy" ie Q.T
TA0

The equation for determining total entropy is FSTOTAL 6 FSSURROUNDINGS @ .ince Q..$::
$GJIGK.

FSSYSTEM

> , Q?8T

Then FSTOTAL 6 > FHBT @ FSSYSTEM This equation shows us that as the temperature increases the value of , Q?8T or Q..$:: decreases" so the effect is less pronounced on Q.T TA0.
$GJIGK.

In the entropy section" one example looked at was the decomposition of calcium carbonate. Jecomposition of calcium carbonate !a! 93s4 !a 3s4 7 ! Q..$::

&3g4

<>>A>-): </

B165 ?@-1mo(-1 B17! 3?mo(-1

$GJIGK.

> ,37%FI48&)I > ,(.E)F kL#,%mol,% 3or ,E)F L#,%mol,%4 > Q..@.TE2 7 Q..$::
$GJIGK.

$sing Q.T Q.T

TA0

TA0

> 37%=E4 7 3,E)F4 > ,'9& L#,%mol,%

$GJIGK.

If this calculation is repeated for a temperature of %(((o!" the effect of the reduced Q..$:: can be seen. Q..$::
$GJIGK.

> ,37%FI48%&F9 > ,(.%'( kL#,%mol,% 3or ,%'( L#,%mol,%4 > Q..@.TE2 7 Q..$::
$GJIGK.

$sing Q.T Q.T

TA0

TA0

> 37%=E4 7 3,%'(4 > 7&E L#,%mol,%

The value of is now positive" showing that the reaction is now feasible. In general raising the temperature of an endothermic reaction makes it more likely to take place and drives an equilibrium to the right.

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A22li,(ti)% )0 R(tes (%* E7+ili&ri(

F(,t)rs e00e,ti%' e7+ili&ri+m ,)%st(%ts
The effect of various factors 3such as temperature and use of a catalyst4 on the position of equilibrium can be found in unit &. Tem2er(t+re In $nit & it was seen that by 0e !hatelierBs principle" increasing the temperature of a reaction causes a shift towards the endothermic reaction. Jecreasing the temperature of a reaction causes a shift towards the exothermic reaction. The explanation for this was seen in the Entropy topic by considering entropy factors in equilibrium reactions. If the forward reaction is exothermic" an increase in temperature favours the reverse reaction" reducing the quantity of product and increasing the quantity of reactant" so the equilibrium constant is reduced. If the forward reaction is endothermic" an increase in temperature favours the forward reaction" reducing the quantity of reactant and increasing the quantity of product" so the equilibrium constant is increased. An increase in temperature always produces an increase in rate. The equilibrium can shift because the proportional increase in rate of the forward and backward reactions will depend upon whether they are endothermic or exothermic. Press+re In $nit & it was seen that by 0e !hatelierBs principle" increasing the pressure of a gaseous reaction causes a shift towards the side with fewer molecules. Jecreasing the pressure of a gaseous reaction causes a shift towards the side with the larger number of molecules. The effect of changing pressure on the equilibrium constant can be seen using a hypothetical example/ A J 7 E If A is &(T dissociated at pressure of % atm" the value of #p can be found. A J 2oles , start % ( 2oles , equilibrium (.I (.& 5artial pressure (.I 8 %.& x% (.& 8 %.& x% > (.=Fatm > (.%F atm #p > 5* x 5J 8 5A > (.%F x (.%F 8 (.=F > (.('%F atm If the pressure is raised the equilibrium would shift to the left. 1hat will this do to the equilibrium constantP At a pressure of & atm the equilibrium shifts to the left so that A is only %'.9T dissociated. A J E 2oles , start % ( ( 2oles , equilibrium (.IEF (.%'9 (.%'9 5artial pressure (. IEF 8 %.%'9 x & (.%'98 %.%'9 x & (.%'98 %.%'9 x & > %.E atm > (.&E atm > (.&E atm #p > 5* x 5J 8 5A > (.&E x (.&E 8 %.E > (.('%F atm E ( (.& (.& 8 %.& x% > (.%F atm

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It can be seen that although the equilibrium has shifted to the left" the equilibrium constant is unchanged. 1hen pressure is increased the molecules are pushed closer together" so effectively the concentration increases. This generally produces an increase in the rate of a reaction. C(t(lyst The presence of a catalyst increases the rate of a reaction of both forward and backward reactions in proportion. This means that the use of a catalyst does not shift an equilibrium in any particular direction and does not change an equilibrium constant.

The table below gives a summary of the effect of changing various conditions on equilibrium. !hange in condition Temperature increase Temperature decrease Temperature increase Temperature decrease 5ressure increase 5ressure decrease 5ressure increase 5ressure decrease !atalyst added :eaction Exothermic Exothermic Endothermic Endothermic 2olecules on 0?. R 2olecules on :?. 2olecules on 0?. R 2olecules on :?. 2olecules on 0?. S 2olecules on :?. 2olecules on 0?. S 2olecules on :?. Effect on Equilibrium Equilibrium position constant .hifts to left Jecreases .hifts to right .hifts to right .hifts to left .hifts to right .hifts to left .hifts to left .hifts to right Go change Increases Increases Jecreases Go change Go change Go change Go change Go change

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I%*+stri(l Pr),esses
Information on entropy change" enthalpy change and equilibrium constants can be used to select conditions for industrial processes. The reaction between nitrogen and hydrogen to produce ammonia is a reversible reaction. G& 7 9?& &G?9 If nitrogen and hydrogen are mixed and heated virtually no ammonia is produced. .ince the value of Q.T TA0 is positive it is clear that the reaction is feasible" so the choice of conditions is key to the production of ammonia in this reaction. It is an exothermic reaction" so a low temperature favours the formation of ammonia. There are two molecules of gas on the right hand side and four on the left" so a high pressure favours the formation of ammonia.

The problem in the production of ammonia is that at the low temperature required for a good equilibrium position" the rate of reaction is so slow as to be non,existent. A high pressure increases the concentration of the gases" and so increases the rate. The problem with creating a pressure is that it is very expensive in terms of building the plant and in terms of maintenance. ?aber devised conditions whereby ammonia could be produced economically. TEMPERATURE PRESSURE ?igh temperature favours good rate 0ow temperature favours equilibrium ?igh pressure favours good rate and good equilibrium 0ow pressure is cheaper 5ressure Temperature !atalyst &E( Atm 'E(o! Iron

TYPICAL CONDITIONS

$nder these conditions ammonia can be produced economically. The use of a catalyst means that a good rate can be produced at a moderate temperature which allows about %( , %E T ammonia to be produced. Although %(T is not a particularly good yield" the unused gases are recycled" so there is no waste" and a rapid reaction means that good quantities of ammonia are produced. In this process as in other industrial processes" the system never actually attains equilibrium. This is because it is more economical to remove the reaction mixture from the reaction vessel when a certain amount of product has formed" separate out the product and recycle to reactants. !hoice of catalyst is very important for the chemical industry. The iron catalyst for the ?aber process becomes more effective when small quantities of other materials called promoters are mixed with the iron.

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The table below shows the effect of promoters on the iron catalyst in the ?aber process at a temperature of '((o! and a pressure of &(( atm. !atalyst Iron Iron Iron 5romoter Gone #& #& 7 Al& T ammonia in exit gases 9AE IA) %9 A %'

A more effective catalyst means that lower temperatures can be used to achieve the same rate" with the result that the equilibrium yield can be increased. Alternatively a lower pressure could be used so making the process less expensive and safer. The chemical industry takes various steps to make reactions more efficient" so saving resources and preventing wastage" thereby making them more sustainable. For example in the ?aber process" with an exothermic reaction" the gases emerging form the reactor are cooled. Incoming gases can be used to do this" which saves energy as these gases do not need to be heated using fossil fuels. The ?aber process has been used as an example of how conditions can be selected to control the reaction and how the process can be made more efficient. These are applicable to the whole chemical industry. In general the chemical industry chooses conditions for a process which makes that process safe and economically effective. Another way in which the creation of a product can be made more efficient is to choose an alternative reaction with improved atom economy.

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A,i* -(se E7+ili&ri(

I%tr)*+,ti)%
Acids occur in natural systems. !itric acid is produced by a number of plants in their fruit. Early investigations of acids found them to have a sour taste. In the nineteenth century a .wedish chemistry by the name of Arrhenius suggested that acid were substances that dissolved in water forming hydrogen ions" ?7. For example in hydrochloric acid" the dissolved hydrogen chloride undergoes the following reaction/ ?!l ?7 7 !l, Arrhenius also proposed that strong acid were fully dissociated into ions" but that weak acids were only partially dissociated. As knowledge of atomic structure grew" it was understood that a hydrogen ions was simply a proton" and that it was unlikely that protons would exist independently in solution. !onsequently it was proposed that the hydrogen ions +oin with water molecules in solution to form the hydroxonium ion" ?9 7. .o the reaction taking place when hydrogen chloride dissolves should be written/ ?!l 7 ?& ?9 7 7 !l, This idea was taken further in the *ronstead 0owry theory of acids.

The -r)%ste(*>L)3ry The)ry

1hen hydrogen bromide is dissolved in water" it forms an acid as the following reaction takes place/ ?*r 7 ?& ?9 7 7 *r, In this reaction the hydrogen bromide transfers a proton to a water molecule. The *ronstead, 0owry theory uses this idea to form a more general theory of acids. According to *ronstead,0owry6 A% (,i* is ( 2r)t)% *)%)r and A &(se is ( 2r)t)% (,,e2t)r9 .o in the reaction between hydrogen bromide and water the ?*r donates a proton to the water" so the ?*r is the acid and the water is acting as a base. Examples6 ?G
9

7 ?&

?9 ?9 ?9

7 G

?!G 7 ?& !?9!

&

7 !G, 7 !?9! ?, ?,
& ,

? 7 ?&

G?9 7 ?& !
&, 9

G?'7 7 ?!
9 ,

7 ?&

These reactions can be regarded as equilibrium. In the reverse reaction the proton moves back in the other direction" so the right hand side of the equation also has a proton donor and a proton acceptor 3or acid and base4. The proton donor and proton acceptor on the right hand side of the equation are called the ,)%I+'(te (,i* and ,)%I+'(te &(se.
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.o ?*r A!IJ Examples A!IJ !?9! ?& ?& ? 7 7 7 ?& *A.E *A.E ?& G?9
9 &,

?9 7 ! GL A!IJ

*r, ! GL *A.E !on+ugate *A.E !?9! ?, ?,

, &

!on+ugate A!IJ ?9
7

&

7 7 7

G?'7 ?!
, 9

7 !

The 2H ,)%,e2t
.ince it is the hydroxonium ion" ?9 7" that causes a material to be acidic" the higher the concentration of this ion" the greater the acidity. The concentration of this ion is measured on the p? scale. This is a log scale defined as follows6 2H 6 >l)';H@< For a strong acid" it is assumed that all the molecules form ?7 ions. Find the p? of 3a4 (.% mol dm,9 ?!l 3b4 (.(% mol dm,9 ?G 3c4 (.& mol dm,9 ?!l 3d4 (.((% mol dm,9 ?I
9

4log ).1 5 1 4log ).)1 5 2 4log ).2 5 )./ 4log ).))1 5 (

N)te A For strong acids a %( fold ditultion 3(.% mol dm,9 to (.(% mol dm,94 results in a p? change of % unit. .ome acids" such as sulphuric are *i&(si,6 this means they can release two hydrogen ions from each molecule. .o a % mol dm,9 solution of H . ' actually has a hydrogen ion concentration of & mol dm,9. Find the p? of 3e4 (.% mol dm,9 ?&. 3f4 (.(% mol dm,9 ?&. [67] 5 ).2 mol dm4(
'

'

6 5 4log ).2 5 )./ 6 5 4log ).)2 5 1./

[67] 5 ).)2 mol dm4(

N)te A nce again a %( fold ditultion 3(.& mol dm,9 to (.(& mol dm,94 results in a p? change of % unit. .ulphuric acid is therefore a strong acid4 As a log scale the p? changes by one unit each time the concentration changes by %( times. C)%,e%tr(ti)% )0 HCO@ i% m)l*m>C
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2H
- 40

% %x%(,% %x%(,& %x%(,9 %x%(,' %x%(,E %x%(,= %x%(,F %x%(,I %x%(,) %x%(,%( %x%(,%% %x%(,%& %x%(,%9 %x%(,%'

) 1 2 ( 3 5 / 1 8 1) 11 12 1( 13

The *iss),i(ti)% ,)%st(%t (i)%i, 2r)*+,t# .3J 0)r 3(ter9

1ater molecules dissociate ?& 7 ? & ?9 7 7 ?, and the concentration of ?9 7 ions at &Eo! is % x %(,F mol dm,9" that is p? F" and this is taken as neutral. This equilibrium exists in any solution in water. If the material is an acid and increases the ?9 7 concentration" the concentration of ?, decreases correspondingly" so that when the ?9 7 concentration is multiplied by the ?, concentration the same value is always obtained. In water the concentration of ?9 .o when the two are multiplied
7

and

?, are both % x %(,F mol dm,9.

% x %(,F x % x %(,F > % x %(,%' mol& dm,=

This value is always the same for any solution in water. It is called the 3(ter *iss),i(ti)% ,)%st(%tJ .39 #w allows us to find the concentration of ?9
7

in alkalis and consequently to calculate their p?.

.3 6 ;HCO@< 1 ;OH>< 6 1 1 1!>14 m)l *m>K And ;?9

7

< >

@w [1/-] 1 % 10-14 0.01

> %&

.o for sodium hydroxide solution of concentration (.(%moldm,9 ;?9

7

< >

> % x %(,%&

p? > ,log3% x %(,%&4

Examples %. For potassium hydroxide solution of concentration (.& mol dm,9.

1 x 10-14
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[6(97] > 6 5 4log 5 # 1)413 5 1(.(

> 5 # 1)413

&. For sodium hydroxide solution of concentration (.(E mol dm,9. [6(9 ] > 41( 6 5 4log 2 # 1) 5 12./ 0.05
7

1 x 10-14

> 2 # 1)41(

Str)%' (%* 3e(8 (,i*s (%* &(ses

The acidity of a solution is measured using the p? scale. If the same concentration of hydrochloric acid and ethanoic acid were taken" they would %)t have the same p? value. This is because the hydrochloric acid *iss),i(tes 3splits up4 ,)m2letely into ?9 7 and !l, ions" whereas only a small fraction of ethanoic acid molecules dissociate. 1hen an acid is fully or near fully dissociated" it is said to be a strong acid" but one which is only slightly dissociated is said to be a weak acid. This should not be confused with concentration of the acid. The same idea applies to bases. A strong base is one in which the particles *iss),i(te ,)m2letely to form hydroxide ions. S)l+ti)% C)%,e%tr(ti)% )0 s)l+ti)% C)%,e%tr(ti)% )0 HCO@ B 2H >C B m)l*m m)l*m>C ?ydrochloric acid (.% (.% % Ethanoic acid (.% (.((%9 &.) ?ydrofluoric acid (.% (.(&' %.= ?ydrocyanic acid (.% (.((((& '.F

E%th(l2y )0 Ne+tr(lis(ti)%
1hen an acid is added to an alkali" there is a temperature change. This is due to the energy produced from the reaction6 ?7 7 ?, ?& the enthalpy for this reaction is ,EF.9kL mol,%. .o whenever a strong acid and a strong base are added together this is the enthalpy change for the reaction. 1ith a weak acid or base the enthalpy change for the reaction is less exothermic than this" as some energy is used in dissociating the acid. St(%*(r* M)l(r E%th(l2y )0 Ne+tr(lis(ti)% ( H%# is the e%th(l2y ,h(%'e 2er m)le )0 3(ter 0)rme* i% the %e+tr(lis(ti)% )0 (% (,i* &y (% (l8(liJ ( "L. (%* 1 (tm#9 Examples :eaction Gitric acid 7 sodium hydroxide ?ydrochloric acid 7 ammonia Ethanoic acid 7 sodium hydroxide ?ydrocyanic acid 7 ammonia Enthalpy change 8kLmol,% ,EF.9 ,E&.& Energy used to dissociate G?9 ,EE.& Energy used to dissociate !?9! &? ,E.' Energy used to dissociate ?!G and G?9

A,i* *iss),i(ti)% ,)%st(%t .(

1e have seen that a strong acid" such as hydrochloric" is one which is fully dissociated. The greater the dissociation" the stronger the acid. The amount of dissociation" and therefore an indication of the strength of an acid" is measured using the dissociation constant.
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The dissociation of an acid is an equilibrium process" and the dissociation constant is derived from the equilibrium constant. The equilibrium expression for the dissociation of acid" ?A" is/ ?A 7 ?& ?9 7 7 A, The equilibrium constant is &c 5 [6(97 ] [*4] [6*] [629]

In a dilute solution the concentration of the water is not going to change significantly during the dissociation process" and so for these reactions it can be taken as constant. [6(97 ] [*4] .o6 &c [629] 5 [6*] This new constant is the acid dissociation constant" #a [ / + &aD'] [* - &aD'] #a > [ /*&aD'] The lower of the acid dissociation constant" #a" the weaker the acid. This equation can then be used to find the p? of a weak acid.

C(l,+l(ti%' the 2H )0 ( 3e(8 (,i*

The acid dissociation expression can be rearranged/ #a ;?A< > ;?9
7

< ;A,<

.ince every molecule of ?A gives one A, ion and one ?9 7 ion" there must be equal numbers of the two ions in any solution" and so ;?9 7< is equal to ; AA<. .ince ;?9
7

< > ;A,<" then

7 &

#a ;?A< > ;?9 .o From the ;?9

7

<

;?9

<

@a [/*]

< the p? can be found6 6 5 4log [6(97] 5 4 log &a [6*]

All these calculations assume that6 i4 because it is a weak acid and only partially dissociated" that the ;?A< does not change significantly on dissociation. ii4 There are no extra ?9 7 ions produced from the water in the acid. Examples Find the p? of the following solutions of ethanoic acid. Ethanoic acid has a #a value of %.FE x %(,E mol dm4( 3a4 % mol dm,9 [6(97] 5 1 # 1./5 # 1)45 5 3.11 # 1)4( moldm4(
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6 5 4 log 3.11 # 1)4( 5 2.(1 3b4 & mol dm,9 [6(97] 5 2 # 1./5 # 1)45 5 5.82 # 1)4( moldm4( 6 5 4 log 5.82 # 1)4( 5 2.2( 3c4 (.% mol dm,9 [6(97] 5 ).1 # 1./5 # 1)45 5 1.(2 # 1)4( moldm4( 6 5 4 log 1.(2# 1)4( 5 2.11 3d4 (.& mol dm,9 [6(97] 5 ).2 # 1./5 # 1)45 5 1.1/# 1)4( moldm4( 6 5 4 log 1.1/ # 1)4( 5 2./( It is possible to find the #a value of an acid by finding the p? of a solution of known concentration. Example 3a4 Gitrous acid of concentration (.% mol dm,9 has a p? of &.%F. !alculate its #a value. [6(97] 5 1)42.1/ 5 -./- #1)4( moldm4(

Ka =

[H3O+]2 [HA]

(6.76 x10-3)2 0.1

= 4.57 x 10-4 moldm-3

3b4 *romic3I4 acid of concentration %.( moldm,9 has a p? of '.9E. !alculate its #a value. [6(97] 5 1)43.(5 5 3.3/ #1)45 moldm4(

Ka =

[H3O+]2 [HA]

(4.47 x10-5)2 1.0

= 2.00 x 10-9 moldm-3

3c4 ?ydrofluoric acid of concentration (.& moldm,9 has a p? of %.)F. !alculate its #a value. [6(97] 5 1)41.8/ 5 ).)1)/ moldm4(

Ka =

[H3O+]2 [HA]

(0.0107)2 0.1

= 5.74 x 10-4 moldm-3

Dil+ti)% )0 Str)%' (%* $e(8 A,i*s

.ince strong acid are fully dissociated" as they are diluted" the hydrogen ions concentration falls in line with the dilution factor. F)r e(,h *il+ti)% )0 1!1J the 2H i%,re(ses &y 1 +%it9 1eak acids are in equilibrium however" and so as they are diluted" some of the undissociated acid molecules split up" so the p? does not increase as fast as it does with the strong acid.
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F)r e(,h *il+ti)% )0 1!1J the 2H i%,re(ses &y !9H +%itJ (%* 0)r e(,h *il+ti)% )0 1!!1J the 2H i%,re(ses &y 1 +%it9 The table below shows how p? changes as an acid is diluted. Jilution factor !oncentration of p? of strong acid ,9 acid 8moldm 3monobasic4 ( (.% % %(x (.(% & %((x (.((% 9 %(((x (.(((% ' p? of weak acid 3monobasic4 &.II 9.9I 9.II '.9I

2.( (%* 2.3 v(l+es

#a and #w quantities are normally very small inconvenient numbers. e.g. #a for ethanoic acid is about %(,E mol dm,9 and #w is about %(,%' mol&dm,=. p#a and p#w give more convenient numbers in the same way that p? values are easier than hydrogen ion concentrations. 2.( 6 >l)'.( 2.3 6 >l)'.3 Examples , Find p#a values for6 3a4 Ethanoic acid 3b4 Gitrous acid 3c4 *romic3I4 acid &a 5 4log 1./5 # 1)45 5 3./&a 5 4log3.5/ # 1)43 5 (.(3 &a 5 4log 2.)) # 1)48 5 1./)

The value of p#w at room temperature is %'. Notice that the smaller the pKa value, the larger the Ka value and the stronger the acid

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A,i*>&(se titr(ti)%s
An acid8base titration is a procedure used in quantitative chemical analysis" in order to determine the concentration of either an acid or a base. Kenerally" an alkaline solution of unknown concentration" and of known volume" is added to a conical flask" by means of a &E.( cm9 pipette. An acid of known concentration is then added to the conical flask using a burette" until the equivalence point is reached" i.e. when the stoichiometric amount of acid has been added to the base" this is when all the alkali has been neutralised and there is no excess acid or alkali present in the solution" this is called the e7+iv(le%,e 2)i%t. Gormally" a visual indicator is used in order to help determine the equivalence point by noticing the exact point at which the colour of the solution changes. The point when the colour changes is the e%* 2)i%t of the titration. If the indicator is chosen correctly the end point and the equivalence point are the same. A p? meter" or conductimetric method" can also be used to determine the equivalence point in an acid8base titration.

2H ,+rves 0)r titr(ti)%s

The characteristic shapes of these curves for the various strong8weak acid8base combinations are shown below" for %( cm9 of (.%( mol dmA9 acid against (.%( mol dmA9 base.
/.(/=a1/ stron# acid/ stron# 6ase pheno(phtha(ein - ok meth+( oran#e - ok ./3.11//=a1/ wea3 acid/ stron# 6ase pheno(phtha(ein - ok meth+( oran#e - no

14 12 10 p/ ! 6 4 2

14 12 10 p/ ! 6 4 2

10

vo(9me o 6ase added/cm

vo(9me o 6ase added/cm3

10

n the left" for ?!l8Ga ?" the p? starts at %" and the curve is almost horiContal up to the endpoint. Then it rises sharply 3end,point > middle of vertical section > about F4 and quickly flattens out again" heading towards p?>%9. f the two most common indicators" methyl )r(%'e changes colour from about 9.E,E.( 3vertical line to left4 and 2he%)l2hth(lei% from about I.E,%(/ either is suitable as it changes completely over the vertical section around %( cm9. n the right" for !?9! ?8Ga ?" the curve starts higher at &.) since the acid is weak" then over the buffer region it rises slowly. The end,point is around p?>I.E"then the latter part of the curve is similar to the first one. nly 2he%)l2hth(lei% is suitable to detect the endpoint/ methyl orange would change very slowly over the buffer region.

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14 12 10 p/ ! 6 4 2

/.(/=/3 stron# acid/ wea3 6ase pheno(phtha(ein - no meth+( oran#e - ok

14 12 10 p/ ! 6 4 2

./3.11//=/3 wea3 acid/ wea3 6ase pheno(phtha(ein - no meth+( oran#e no

10

10

vo(9me o 6ase added/cm3

vo(9me o 6ase added/cm3

n the left" strong acid against weak base can be titrated using methyl )r(%'e. 1hile" on the right the weak acid and base give no sharp endpoint and there is no suitable indicator.

.ummary/ using a weak base" like ammonia" phenolphthalein is unsuitable because it doesnBt start to change until after the endpoint. using a weak acid" like ethanoic acid" methyl orange is unsuitable because it changes steadily" and change is complete before the endpoint.

Determi%i%' 2.( (%* .( 0r)m titr(ti)% ,+rves

1hen a weak acid is titrated with a strong base" the following curve is obtained.

In the reaction/ ?A 7 ?, A, 7 ?& At half way to the end point" ;?A< > ;A,< 7 , 7 ;? < ;%< 4 [/31B] 9 @a 4 ;?9 < ;A < 4 ;?A< ;%< Taking logs Alog #a > ,log ;?9
7

<

.o p#a > p? 3X half neutraliCation4

Half way o !" "#d $o%#

p#a > p? at half neutraliCation #a > antilog , p#a p? at half neutraliCation is '.I.

e.g. For ethanoic acid

#a > antilog ,p? > antilog ,'.I > 19HL 1 1!>H m)l *m>C
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Ch)i,e )0 i%*i,(t)r 0r)m 2.I% v(l+es

.odium ethanoate is the salt formed from ethanoic acid A a weak acid" and sodium hydroxide A a strong base. 1hen it is placed in water it splits up completely into ions. .ome water molecules also are dissociated" so the solution contains Ga7" !?9! &," ?7 and ?,. Ethanoate ions and hydrogen ions tend to +oin to form undissociated ethanoic acid" leaving an excess of hydroxide ions.

=aB /B

./3.121/-.

=aB

./3.12/ 1/-.

This means that a solution of sodium ethanoate isin fact alkaline. This is the case for any salt made from a weak acid and a strong base. In the same way a salt made from a strong acid and a weak base is acidic in solution. This means that at the point of neutralisation the p? is not F. 1hen carrying out titrations using weak acid and strong base an appropriate indicator must be selected. Titr(ti)% I%*i,(t)r .trong acid 7 strong alkali *romothymol blue 1eak acid 7 strong alkali 5henolphthalein .trong acid 7 weak alkali 2ethyl orange In a titration" when the moles of acid and moles of alkali are exactly the same" it is said to be at the e7+iv(le%,e 2)i%t9 The point at which the indicator changes colour is the e%* 2)i%t. It is clearly important that for a particular titration the end point should be the same as the equivalence point. An indicator is in fact a weak acid" ?In. 0ike other weak acids" it dissociates" so it forms ?7 and In, ions. The ?In will be one colour and the In, will be a different colour. ?In ?7 7 In, !olour % !olour & In an acid solution" the high concentration of ?7 will cause the equilibrium to move to the left" and so it will be colour %. 1hen in alkali solution" the ?7 will be removed and the equilibrium will shift to the right and become colour &. 1hen the amount of ?in and are exactly balanced the colour will be in between the two colours. ne drop of acid or alkali" and the equivalence point should be able to change the colour of the indicator.

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The end point for a particular indicator can be found. As a weak acid" the #a" or #In expression can be written #In > At the end point" ;In,< > ;?In<" And ;?7< > #In ,log ;?7< > ,log #In p? > p#In .o the end point for any indicator takes place at a p? equal to its 5kIn value. To choose an indicator the p#In value must be in the right p? range for the titration being done. e.g. methyl orange p#In > E.% for p? range '.& , =.9 3p#In 7 or , one p? unit4 .trong acid and strong base , any indicator. .trong acid and weak base , low p? range 9.%, '.' e.g. methyl orange. 1eak acid and strong base , high p? range I.9 , %(.( e.g. phenolphthalein. 1eak acid and weak base , narrow p? range" very hard choice.

[/B][7n-] [/7n ]
so ;In,< 8 ;?In< > %

In each case p#In must be matched to p? at equivalence point of titration. E%* 2)i%t > mid way between & colours of indicator 3a property of the indicator4. E7+iv(le%,e 2)i%t > when the stoichiometric amounts of acid and alkali have been added. End point and equivalence point must coincide for an effective titration. C)l)+rs/ Phe%)l2hth(lei%/ colourless from % to I.E" turns pink from I.E to %(" remains pink above %(. Methyl )r(%'e= red from % to 9.E" then changes from red through orange to yellow between 9.E and E.(6 yellow from E.( to %'.

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-+00er S)l+ti)%s
A buffer solution contains a weak acid or weak base and one of its salts. It resists dramatic changes in p? if small quantities of acid or alkali is added to it. Examples6 3i4 a weak acid with its sodium salt 3or similar4 e.g. ethanoic acid and sodium ethanoate" A giving high concentrations of !?9! ? molecules and !?9! ions. 3ii4 a weak base with one of its salts e.g. ammonia and ammonium chloride" giving high concentrations of G?9 molecules and G?'7 ions. !onsidering the dissociation of ethanoic acid" in the buffer we have deliberately made the A concentrations of !?9! ? molecules and !?9! ions large" and this determines the 7 concentration of ? ions" and so the p?. CHCCOOH H@ @ CHCCOO/ 1hen a little additional strong acid is added" most of the ? 7 ions react with some of the ethanoate to form ethanoic acid/ H@ @ CHCCOO/ CHCCOOH Therefore the concentration of ?7 in the solution only rises slightly" and there is a very small drop in p?. Although the ;CHCCOO/< decreases" it only does so by a small amount compared to the siCe of the reservoir of CHCCOO/ in the buffer" so the p? remains relatively constant. !onversely" if some alkali is added" most of the ?A ions react with !?9! OH/ @ CHCCOOH H O @ CHCCOO/ ? molecules/

This time the ?7 doesnBt fall by nearly as much as expected" and the p? remains relatively constant. Although the ;CHCCOO/< increases" it only does so by a small amount compared to the siCe of the reservoir of CHCCOO/ in the buffer. ?A/

In the G?98G?'!l buffer" the G?9 reacts with ?7" and the ammonium ions react with H@ @ NHC NH4@ OH/ @ NH4@ H O @ NHC

*uffered solutions do change in p? upon addition of ?7 or ?, ions. ?owever" the change is much less than that would occur if no buffer were present.

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C(l,+l(ti%' the 2H )0 ( &+00er s)l+ti)%

:i; 6 of a buffer solution containing ).5)) mol dm =( sodium ethanoate and =( ).1)) mol dm ethanoic acid :&a 5 1./3 1)=5 mol dm=(;0 <hat is the

In a buffer made up from a mixture of ?A and GaA" it is a very good approximation that all of the acid ?A will be undissociated" and all the AA will come from the salt/ ;?A< > conc. of acid6 ;AA< > conc. of salt Then/ from which #a >
[/ + ] [* - ] > [/*]

[/ + ] 0.500 > %.F' H %(AE mol dmA9 0.!00

;?7< > &.FI H %(AE mol dmA9" and p? > 49HK

In the alternative method" the He%*ers)%>H(ssel&(,h equation is derived as follows from the dissociation constant expression for the weak acid used in the buffer 3representing the acid as ?A4/ #a > Taking logs gives
[/ + ] [* - ] [/*]

log #a

>

log;?7< 7 log

[* ] [/*]

and so or

Alog #a p#a

[* ] 7 > Alog;? < A log [/*]

>

p?

A log

[* ] [/*] [* ] [/*]

from which

p?

>

p#a

log

.ince the acid is weak it is present almost entirely in the form of molecules" and virtually all the A AA comes from the salt present6 so" to a good approximation" ;A < is the same as the concentration of the salt and ;?A< is the same as the concentration of the acid" giving 2H 6 2.( @ l)' [concentration o acid] from which it is clear that if the concentration of salt is equal to the concentration of acid" the p? of the buffer is equal to p#a for the acid.
[concentration o sa(t ]

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Examples using pKa$ :ii; <hat is the 6 of the solution obtained when 31g of sodium ethanoate is dissol!ed in 1dm =( of ).1)) mol dm ethanoic acid : &a 5 3./-;0 2olar mass of !?9! Amount of !?9! p? > I& g molA% 41 # Ga in '%g > > (.E(( mol6 conc. > (.E(( mol dmA9 !2 # mo( -1 Ga (

[* ] [/*] 0.500 > '.F= 7 log > 49HK 0.!00

> p#a 7 log

:ii; <hat is the 6 of the buffer solution obtained when 1)) cm ( of ).1)) mol dm=( ethanoic acid is mi#ed with 2)cm( of ).()) mol dm( sodium ethanoate solution0
100 H (.%(( 1000 20 Amount of sodium ethanoate > H (.9(( 1000

Amount of ethanoic acid

>

> (.(%(( mol > (.((=( mol > 49H4

p?

> p#a 7 log [* ] > '.F= 7 log 0.0060 0.0100 [/*]

-+00eri%' -i)l)'i,(l Systems

In order to work effectively blood needs to be at a p? of F.'. This p? is maintained by a number of buffering systems including plasma" proteins" haemoglobin and carbonate8hydrogencarbonate con+ugate acid,base pairs. The proteins are able to act as buffers because of the amine and carboxylic acid side chains of the amino acids composing them. The carbonate8hydrogencarbonate con+ugate acid,base pairs buffer the blood by the equilibrium/ ?&! 93aq4 ?! 9,3aq4 7 ?73aq4 If the p? of the blood drops" as ?7 increases" this equilibrium shifts to the left reducing the ?7 again and consequently raising the blood p?. n its own this equilibrium would be of limited value as the increasing level of ?&! 9 would mean that the movement to the left would stop" but there is a second equilibrium involving the ?&! 9/ ?&! 93aq4 ! &3aq4 7 ?& 3l4 At the level of ?&! 9 increases it produces carbon dioxide which is then removed by gas exchange in the lungs. If the p? of the blood increases" as ?7 decreases" the ?&! 93aq48?! 9,3aq4 equilibrium shifts to the right increasing the ?7 again and consequently lowering the blood p?.

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Chir(lityJ C(r&)%yls (%* C(r&)1yli, A,i*s

I9estions on this 9nit ma+ inc(9de materia( rom ;=7- 2 see s+((a69s Is)merism
Str+,t+r(l is)merism9 .tructural isomerism was dealt with in $GIT &. All isomers are compounds with the same molecular formula. e.g. !'?%( or !&?= . .tructural isomers have atoms arranged in different orders. They have similar bptYs. e.g. !?9!?&!?&!?9 3butane4 and !?9!?3!?94!?9 3&,methylpropane4 !?9!?& ? 3ethanol4 and !?9 !?9 3methoxymethane4 Stere)is)merism9 .tereoisomers have the same molecular formula and the same structural formula. The same atoms are arranged in the same order but with different orientations in space. Ge)metri," cis,trans" or E,Z isomerism , also dealt with in $GIT & , is one form of stereoisomerism. Another form is )2ti,(l isomerism.

Chir(lity
!hirality leads to optical isomerism. ptical isomerism occurs when two compounds have the same molecular formula" but are not superimposable on each other. If a compound contains a carbon atom bonded to four different groups or atoms" it can exist in two forms which are mirror images of each other. Example !?9!?3 ?4! %6(%6:96;%926
&

. /1 /3. .12/ /12.

. 1/ ./3

The two isomers affect polarised light by r)t(ti%' the 2l(%e )0 2)l(ris(ti)% )0 2l(%e 2)l(rise* m)%),hr)m(ti, li'ht i% )22)site *ire,ti)%sM this is where the term [optical[ comes from. ptical isomers differ only in the extent to which they rotate the plane of polarised monochromatic light. ptical isomers exist in two forms called e%(%ti)mers. The dextrorotatory 374 form rotates light to the right 3clockwise4 but the laevorotatory 3,4 rotates light to the left. A sample of an optically active substance may contain both optically active isomers. An equimolar mixture does not rotate light at all as equal and opposite rotations cancel. This optically inactive mixture is called the r(,emi, mi1t+re or racemate. The carbon atom with four different groups around it 3the ,hir(l ,e%tre4 is said to be (ssymetri,9 The two mirror image molecules are said to be ,hir(l.
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C(r&)%yl C)m2)+%*s
I%tr)*+,ti)%
!arbonyl compounds contain the !> group. 1hen this group occurs at the end of a carbon chain" the compound is an aldehyde 3:!? 4" the name ending in Aal. 1hen group occurs within the carbon chain" the compound is a ketone 3:! :%4" the name ending in Aone.

/ / . / / / . /

/ / . . / / Gentana( / . / / .

/ . /

1 . / 1 . /

/ / . / / / . /

1 / / . . . / / Gentan-3-one 1 . / .

/ . / / / . / /

/ . / 2-:eth+(69tana( /

/ . / 3-:eth+(69tan-2-one /

The carbonyl group in polar because of the electronegative oxygen atom. o The geometry around the carbonyl group is planar" with bond angles of about %&( .

Physi,(l Pr)2erties
!arbonyl compounds are much more volatile than the corresponding alcohol because" unlike alcohols" they do not have any hydrogen bonding. They are less volatile than an alkane of similar formula mass because of the polarity of the molecules. !ompound Formula Formula mass *oiling point 8o! 5ropane !9?I '' ,'& Ethanal !?9!? '' &( Ethanol !&?E ? '= FI Although carbonyl compounds do not have a hydrogen which is directly connected to the oxygen" and therefore they have no hydrogen bonding" when placed in water the oxygen in the carbonyl is able to form a hydrogen bond with the hydrogen in the water molecules. This makes the carbonyl compounds" especially those with short carbon chains" very soluble in 1ater.

Chemi,(l Pr)2erties
Aldehydes and ketones are both attacked by nucleophiles" and can both be reduced to alcohols. ?owever" only aldehydes can be readily oxidised" and this is the basis for tests to distinguish between them. Aldehydes and ketones are obtained by oxidation of primary and secondary alcohols" respectively.

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The test 0)r ( ,(r&)%yl 'r)+29

All carbonyl compounds react with &"',dinitrophenylhydraCine 3*radyYs reagent4. 1hen a solution of &"',dinitrophenylhydraCine is added to a carbonyl" a reaction takes place at room temperature producing orange crystals. This is used as the test for the presence of the carbonyl group. Ethanal and &"',dinitrophenylhydraCine

./3 /

=12 . 1 /2= =/ =12

./3 /

=12 . = =/ B /2 1 =12

5ropanone and &"',dinitrophenylhydraCine

./3 ./3

=12 . 1 /2= =/ =12

./3 ./3

=12 . = =/ B /2 1 =12

5ropanal and &"',dinitrophenylhydraCine

.2/5 /

=12 . 1 /2= =/ =12

.2/5 /

=12 . = =/ B /2 1 =12

O1i*(ti)%
Aldehydes are reducing compounds and can react with some oxidising agents. .ince ketone cannot be oxidised" they do not take part in oxidation reactions. This is used as a test for distinguishing between aldehydes and ketones. Aldehydes will react when heated with ammoniacal silver nitrate solution 3T)lle%Ns re('e%t4. This is a reaction in which the aldehyde is oxidised" and the silver ions are reduced to silver. 1hen carried out in a clean test tube it forms a silver mirror. RCHO((7# @ A'(NHC# @((7# @ H O RCOOH((7# @ A'(s# @ NH4@((7# .ilver mirror

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Aldehydes will also react with other oxidiCing agents. These tests are summariCed below6 O1i*isi%' ('e%t

T)lle%Os re('e%t Fehli%'Os s)l+ti)% Di,hr)m(te s)l+ti)%

C)%*iti)%s ?eat aldehyde with ammoniacal silver nitrate ?eat aldehyde with FehlingBs solution ?eat aldehyde with a mixture of potassium dichromate solution and sulphuric acid

Res+lt 0)r (l*ehy*e .ilver mirror forms Turns from a blue solution to form a red precipitate Turns from an orange solution to a green solution

Al*ehy*es 3ith Fehli%'Os s)l+ti)% ()1i*(ti)%# Aldehydes 3but not ketones4 reduce !u&7 to !u7 giving a red brown precipitate of copper 3I4 oxide in this test. Jrops of the carbonyl compound are added to equal volumes of FehlingYs solutions A and *. The mixture is warmed in a water bath. 3oxidation4 RCHO((7# @ C+ @((7# @ H O(l# RCOOH((7# @ 4H@((7# @C+ O(s#

Re*+,ti)%
!arbonyl compounds are formed by oxidation of alcohols. The reverse of this process" reduction" converts carbonyls back into alcohols;\<. This reduction can be carried out by reducing agents such as lithi+m tetr(hy*ri*)(l+mi%(te(III# 3lithium aluminium hydride] 3ith *ry ether as a solvent or sodium tetrahydridoborate3III4 3sodium borohydride] in water. N)te , In equations showing reduction the reducing agent is written as ;?<. e.g. The reduction of propanal to propan,%,ol. %6(%62%69 7 2[6] %6(%62%6296 %6(%6:96;%6(

The reduction of propanone to propan,&,ol. %6(%9%6( 7 2[6]

N+,le)2hili, (**iti)%
!arbonyl compounds with the !> group" can undergo (**iti)% reactions. In this case the attack is by a %+,le)2hile being drawn to the molecule by the partial positive charge on the carbon. ?ydrogen cyanide will add on across the !> bond. To carry out this reaction" a mixture of 2)t(ssi+m ,y(%i*e (%* eth(%)i, (,i* is used to avoid use of the very poisonous hydrogen cyanide. These reactions take place at r))m tem2er(t+re with the mixture &+00ere* (t 2H L. Ethanal and ?!G

1 . B @.=J p/ ! &/.=' / /3.

1/ ./ .=

/3.

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5ropanone and ?!G

1 /3.
Re(,ti)% me,h(%ism

1/ B @.=J p/ ! &/.=' ./
3

/3.

. ./3

.=

In this reaction the initial attack is by the cyanide ion. The cyanide ion is a nucleophile which is attracted to the partial positive charge on the carbonyl carbon created by the electronegative oxygen. The reaction has to be carried out in slightly basic conditions" so the mixture is buffered at p?I. This is to allow the formation of the cyanide ion from the hydrogen cyanide. ?!G ?7 7 !G,

If the p? is lower than I" the dissociation of the ?!G lies too far to the left and so the concentration of !G, is too low for the first step to take place.

/3 .

/3 . .
B

/B

-.

=. /

-.

/3. =. / . 1/

If the p? is higher than I" the concentration of ?7 ions is too low for the second stage of the mechanism to take place.

Re(,ti)% )0 i)*i%e i% (l8(li

Iodine in alkali reacts with a specific group" !?9! : to produce a yellow precipitate of !I9?. :! & is also formed in this reaction. This is used as a test for the presence of the !?9! : group. 3Ethanal" ethanol or any methyl 8et)%e can react in this reaction4. The iodine present in the testing reagent can oxidise alcohols" and so !?9!? ?: will initially form !?9! : this will then react to give the yellow crystals. The old name for these crystals of triiodomethane is iodoform" and this reaction is often referred to as the iodoform reaction. The test is carried out by adding aqueous sodium hydroxide to iodine solution until the mixture +ust turns colourless. The organic material is then added" and the mixture is warmed. !?9! : and !?9!? ?: give a positive iodoform reaction 3where : can be a carbon chain or hydrogen4. 1hich of the following will give a positive iodoform reactionP !?9!?&!? !?9!? ?!?9 >o ?es !?9!?&! !?9 ?!? ?es >o

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C(r&)1yli, (,i*s
I%tr)*+,ti)%
!arboxylic acids are compounds containing the carboxyl group" ! &?" which consists of the !> group and the ? group on the same carbon. The name carboxyl comes from a combination of the names of these functional groups6 !arbonyl 7 hydroxyl > !arboxyl

/ / . /

5ropanoic acid

/ . /

1 . 1 / 1 . 1 /

/ / . / / / . /

*utanoic acid

/ . /

/ . / / . /

1 . 1 1 . 1 / /

/ / . /

/ . /

/ . / . / /

/ . / . / /

&,2ethylbutanoic acid

9,2ethylbutanoic acid

Physi,(l Pr)2erties
The !arboxyl carbon contains two oxygen atoms both of which are electronegative leaving the carbon with a partial positive charge. This allows carboxylic acids to form stronger hydrogen than alcohols" and they therefore have higher boiling pints than alcohols of similar formula mass. C)m2)+%* 5ropanol Ethanoic acid F)rm+l( !?9!?&!?& ? !?9! &? RFM =( =( -)ili%' 2)i%t B)C )F %%I

The structure of the carboxyl group allows carboxylic acid to form dimers

1 , . 1

/ /

1 . 1 ,

Ethanoic acid has a melting temperature of %Fo!" so if the temperature falls below this it freeCes" and the similarity of froCen ethanoic acid to ice has given the pure acid the common name of 'l(,i(l eth(%)i, (,i*. The ability of carboxylic acids to form hydrogen bonds means that the lower members of the homologous series 3those with up to ' carbon atoms4 are miscible in all proportions with water. The longer the carbon chain" the less soluble in water the carboxylic acid becomes.

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Pre2(r(ti)% )0 ,(r&)1yli, (,i*s

!arboxylic acids can be prepared by xidation of primary alcohols xidation of aldehydes ?ydrolysis of nitriles Pre2(r(ti)% 0r)m 2rim(ry (l,)h)ls 1hen a primary alcohol is heated under reflux with potassium dichromate and sulphuric acid a carboxylic acid is produced. :!?& ? 7 &; < :! &? 7 ?& Pre2(r(ti)% 0r)m (l*ehy*es 1hen an aldehyde is heated under reflux with potassium dichromate and sulphuric acid a carboxylic acid is produced. :!? 7 ; < :! &? Pre2(r(ti)% 0r)m %itriles !arboxylic acids can be formed by hydrolysis of nitrile 3:!G4 compounds. The hydrolysis can be carried out by heating the nitrile with acid or alkali. Hy*r)lysis +si%' *il+te hy*r),hl)ri, (,i*9 :!G 7 &?& 7 ?!l :! &? 7 G?'!l Hy*r)lysis +si%' (7+e)+s s)*i+m hy*r)1i*e 2r)*+,es the s(lt )0 the ,(r&)1yli, (,i*9 :!G 7 ?& 7 Ga ? :! &Ga 7 G?9 The acid can be obtained from the salt by adding a strong acid. :! &Ga 7 ?!l :! &? 7 Ga!l

Chemi,(l Pr)2erties
Re*+,ti)%
!arboxylic acids are formed by the oxidation of primary alcohols" and can be converted back to these compounds using lithium tetrahydridoaluminate3III4 3lithium aluminium hydride] as a reducing agent. The acid is treated with lithium aluminium hydride in ether" followed by the addition of water. e.g. :eduction of propanoic acid. :eduction of methanoic acid. %6(%62%926 7 3[6] 6%926 7 3[6]

%6(%62%6296 7 629 %6(96 7 629

Re(,ti)% 3ith (l,)h)ls

!arboxylic acids react with alcohols in the presence of concentrated sulphuric acid to form water and an ester. The carboxylic acid is mixed with alcohol and concentrated sulphuric acid is added. The mixture is then warmed. :! ? 7 :\ ? :! :\ 7 ?& e.g. 5ropanoic acid 7 ethanol %6(%62%926 7 %6(%6296 %6(%62%99%62%6( 7 629 Ethyl 2r)2(%)(te

Esters are named from the (l8yl group of the alcohol and the /)(te from the carboxylic acid.
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The esters formed contain the ester 0+%,ti)%(l 'r)+2 or ester link. This has the structure shown below. :! ? 7 :\ ? :! :\ 7 ?&

1 , . 1 ,K Ester group

Esters have characteristic odours" which makes them useful for flavouring. 5ear drops and pineapple flavourings are derived from the appropriate ester. Esters are also useful as solvents. Re(,ti)% 3ith 2h)s2h)r+s 2e%t(,hl)ri*e The , ? group in the acid will react with halogenating reagents" such as phosphorus pentachloride in the same way as the ? group in alcohols. These reactions occur at room temperature. The organic product of these reactions are (,yl ,hl)ri*es 3or acid chlorides4. This functional group has the structure shown below.

1 , . .(
Ethanoic acid reacts with phosphorus pentachloride to produce ethanoyl chloride. !?9! &? 7 5!lE !?9! !l 7 ?!l 7 5 !l9 Ethanoyl chloride 5ropanoic acid reacts with phosphorus pentachloride to produce propanoyl chloride. !?9!?&! &? 7 5!lE !?9!?&! !l 7 ?!l 7 @9%l( 5ropanoyl chloride

Acyl chloride group

Ne+tr(lis(ti)% re(,ti)%s
!arboxylic acids react with alkalis" carbonates and hydrogencarbonates to form salts. Re(,ti)% 3ith s)*i+m hy*r)1i*e Re(,ti)% 3ith s)*i+m ,(r&)%(te9 :! &:!
&

? 7 Ga ? ? 7 Ga&!
9

:!

, &

Ga7 7 ?&
,

&

&:! :!

&

Ga7 7 ?&

7 ! 7 !

&

Re(,ti)% 3ith s)*i+m hy*r)'e%,(r&)%(te :! &? 7 Ga?!

&

Ga7 7 ?&

&

.uch reactions" using titration with a known concentration of alkali and appropriate indicator" can be used to determine the quantity of acid present. For example this technique can be used to find the quantity of citric acid in fruit.

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Deriv(tives )0 C(r&)1yli, (,i*s

rganic compounds made from carboxylic acids are called derivatives of carboxylic acids. This includes (,yl ,hl)ri*es and esters.

Esters
The ester functional group is

1 , . 1 ,K

Esters can be hydrolysed by boiling with acid or alkali. 1hen hydrolysed by acid" the alcohol and the carboxylic acid are reformed. This is a reversible reaction" so does not go to completion. :%! :& 7 ?& :%! &? 7 :& ? 1hen hydrolysed by an alkali" the alcohol and the salt of the carboxylic acid are formed. .ince the carboxylic acid is not formed" this reaction can go to completion. .uch a reaction is called s(2)%i0i,(ti)%. :%! :& 7 Ga ? :%!
& ,

Ga7 7 :& ? !?9!?&! ? 7 !?9!?& ?

e.g. Acid hydrolysis of !?9!?&! &!?&!?9 !?9!?&! &!?&!?9 7 ?&

&

?ydrolysis of !?9!?&! &!?&!?9 by sodium hydroxide solution !?9!?&! &!?&!?9 7 Ga ? !?9!?&! &,Ga7 7 !?9!?& ? Acid hydrolysis of 3!?949! ! !?9 3!?949! ! !?9 7 ?& !?9! ? 7 3!?949! ?

&

?ydrolysis of 3!?949! ! !?9 by sodium hydroxide solution 3!?949! ! !?9 7 Ga ? !?9! &,Ga7 7 3!?949! ? The reaction of natural esters with sodium hydroxide solution is used to make soap. An animal fat is an ester formed from propan,%"&"9,triol and carboxylic acids with long chains. !?&A A! A!%F?9E ?A!A A! A!%F?9E !?&A A! A!%F?9E *nimal fat 7 9# ? !?&A ? ?A!A ? 7 9 !%F?9E! !?&A ? gl'cerol
,

#7

stearate salt 5 A9*@

The products on saponification are propan,%"&"9,triol and the salt of the carboxylic acid.

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The structure of the salt of the carboxylic acid is shown below.

+ =a

- 1 1 .

The charges on the molecule give the useful properties of soap. The charged section is attracted to the polar water molecules A is hy*r)2hili,. The hydrocarbon section is repelled by the water molecules A is hy*r)2h)&i,. The soap molecule can be pictured as like a tadpole with Nhydrophilic headO and Nhydrophobic tailO.

8ater

The hydrophilic head is attracted into the water and the hydrophobic tail is repelled by water so the molecules arrange themselves as shown here. This breaks down the surface tension of the water and allows it to wet a surface.

P)lyesters
The reaction of an alcohol and a carboxylic acid to form an ester can be used to form polymers in which the monomers are +oined by an ester link. .uch a polymer is called a 2)lyester. This is an example of a ,)%*e%s(ti)% 2)lymer in which monomers +oin by e+ecting a small molecule 3water in the case of a polyester4. n? !?&!?& ? 7 n? &!,!=?',! &? ethane,%"&,diol benCene,%"', dicarboxylic acid ,3,!?&!?&, ,! ,!=?',! , ,4,n 7 n?& Terylene

Tr(%sesteri0i,(ti)%
The burning of diesel oil from petroleum is not an environmentally s+st(i%(&le method of providing energy. An alternative is to use natural oils from plants that are renewable. .uch oils will only partially combust in a normal diesel engine" and will therefore cause clogging of the engine. Engines can be modified to burn this type of fuel. An alternative is to convert the triglyceride in the fat or oil to a methyl ester. The methyl ester is more volatile and can be used in a normal diesel engine. The methyl ester can be formed in a process called transesterification. 2ost biodiesel is produced by &(se>,(t(lyse* tr(%sesteri0i,(ti)%
1 /2. 1 . 1 /. 1 . /2. 1 . 1

B 3./31/

/2. /. /2.

1/ 1/ 1/ 3 /3. 1 1 . Eio Fiese(

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A,yl ,hl)ri*es
The acyl chloride functional group is

1 , . .(
Acid chlorides are highly reactive compounds. They are readily hydrolysed at room temperature" and will fume in moist air due to this reaction. Important reactions of acyl chlorides are6 ?ydrolysis 3reaction with water4 :eaction with alcohols :eaction with concentrated ammonia :eaction with amines

Hy*r)lysis
In hydrolysis the acid chloride is converted to the carboxylic acid and ?!l is produced. :eaction with water :! !l 7 ?& :! &? 7 ?!l

Re(,ti)% 3ith (l,)h)ls

They react with alcohols at room temperature to produce the ester. :! !l 7 :^ ? :! :^ 7 ?!l

Re(,ti)% 3ith ,)%,e%tr(te* (mm)%i(

They react with concentrated ammonia at room temperature to produce (,i* (mi*es. :! !l 7 G?9 :! G?& 7 ?!l

Re(,ti)% 3ith (mi%es

They react with amines at room temperature to produce secondary substituted amides. An amine is a a carbon chain attached to the G?& functional group. :! !l 7 :^G?& :! ,G?,:^

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S2e,tr)s,)2y (%* Chr)m(t)'r(2hy

I%tr)*+,ti)%
Disible light is one very small part of the electromagnetic spectrum. The different properties of the various types of radiation depend upon their wavelength. The diagram below shows a crude illustration of the various types of radiation of relevance to chemists

8ave(en#th decreasin# HreD9enc+ increasin# )ner#+ increasin#

:icrowaves

,adio waves

7n ra red

Lisi6(e (i#ht

;(tra vio(et

In the $nit & section on .pectroscopy the use of i%0r( re* s2e,tr)s,)2y and m(ss s2e,tr)s,)2y in analysis were looked at. The use of infra red spectroscopy to determine the extent of a reaction involving a change in functional group was also examined. #nowledge and understanding of these aspects are included in this topic of $nit '.

N+,le(r M('%eti, Res)%(%,e S2e,tr)s,)2y

?ydrogen atoms can be detected using this sort of spectrometry. Any spinning charge generates a magnetic field" so the protons in a nucleus have a magnetic field. If there are two protons in a nucleus they will have opposite spins so the magnetic fields cancel. Gay nucleus with an even number of protons will have no overall magnetic field" but a nucleus with an odd number of protons will have a resultant magnetic field. 1hen a nucleus with a resultant magnetic field is placed in a strong magnetic field it will align itself with that field.

>pinnin# proton Groton ie(d )%terna( ie(d

If the proton supplied with sufficient energy it can flip to a position opposing the external field. The energy required to do this lies in the radio frequency region of the electromagnetic spectrum.

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In a high energy position the magnetic field of the proton is opposed to the external magnetic field.

Energy

The energy required to flip the proton lies in the radio frequency region.

In a low energy position the magnetic field of the proton is aligned with the external magnetic field. The actual energy required depends upon the exact environment on the proton. In nuclear magnetic resonance" NMR" spectroscopy a substance is placed in a strong magnetic field and sub+ected to a range of radio frequencies. The point at which a particular radio frequency is absorbed will depend upon the environments of the protons present in that substance.

,adio reD9enc+ detector )%terna( ma#netic ie(d >amp(e

,adio reD9enc+ #enerator

The detector will show which radio frequencies are absorbed. The system is calibrated" usually using the compound tetr(methylsil(%eJ Si(CHC#4J as the ( point and then other frequencies compared to this as shift values. .elected shift values are given in the table below. ?ydrogen environment shift !H9,: (.) :,!H&,: %.9 :9!H &.( ,!> ,!H9,: &.9 :,!H&, ? 9.= : H '.E ,!H ).E

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NMR s2e,tr(9
The number of protons that can be found in each environment are given by area under the line and defined by the integration trace. A simplified nmr for propanal is shown below.

3 1 2
The peak at ).) shows The peak at &.9 shows The peak at (.) shows ,!H ,!> ,!H9,: !H9,:

11 10 $

5 4

?igh resolution G2: spectrum give further information about the proton environment.

3 3

The field experienced by this proton will be affected by the two protons on the ad+acent carbon.

/K / . . /

a
These protons can affect the field at ?\ according to whether they are aligned with the field or against it.

6
Gumber with this alignment % & %

The effects are shown in the table below6 a b Alignment & against field % with field %against field % with field %against field & with field

This means that when looked at in high resolution the following pattern is seen A triplet at ratio %/&/% indicates that ad+acent carbon

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If there are three protons on the ad+acent carbon a b c Alignment 9 against the field & against the field % with the field & against the field % with the field & against the field % with the field % against the field & with the field % against the field & with the field % against the field & with the field 9 with the field Gumber with this alignment % 9

A quadruplet at ratio %/9/9/% indicates that there are three protons on the ad+acent carbon

Uses )0 NMR
!learly G2: is important for chemical analysis. It also has useful applications in medicine. The principle of nuclear magnetic resonance is used in 2agnetic :esonance Imaging" 2:I" body scanners which detect the protons in water molecules in the body. This process" unlike the use of M,rays is thought to be completely harmless to patients. Guclear magnetic resonance can be used to determine the purity of pharmaceutical products.

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Chr)m(t)'r(2hy
.imple paper chromatography can be used to separate a mixture of dyes. The principle on which this works are also useful for more sophisticated techniques. Essentially any form of chromatography used a fixed material 3stationary phase4 and moving substance 3mobile phase4. The separation occurs due to the equilibrium between the components in the mixture and the stationary and mobile phases.

:o6i(e phase >tationar+ phase :o6i(e phase >tationar+ phase

The low concentration of the material in the liquid 3at A4 causes the material to dissolve

The liquid carries the dissolved material forward. The low concentration of the material at * causes the material to be adsorbed into the stationary phase.

The process continues in this way" the rate of movement determined by the equilibrium movement which depends upon the strength of the interaction of the material with the stationary phase and its solubility in the solvent in the mobile phase.

C)l+m% ,hr)m(t)'r(2hy
ne version of this technique is column chromatography. In this process a column is packed with an adsorbent solid" such as alumina. The mixture is then placed in the top of the column so that it is adsorbed onto the surface of the solid. The solvent 3or el+e%t4 is then poured into the top and allowed to trickle through the column. 5artition of the solutes between the moving solvent and the stationery phase takes place. The rate at which the solute moves down the column depends upon its partition coefficient.
)(9ent adsor6ent Eands o separated components

>intered #(ass disc

If the component is coloured" it is clear when it emerged from the column. If can be collected and the solvent evaporated to obtain the pure substance. If the substance is colourless" there are other ways of detecting their presence" for example certain materials glow in ultra,violet light.

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Hi'h>Per0)rm(%,e Li7+i* Chr)m(t)'r(2hy

The effectiveness of column chromatography can be improved by using a very fine powder as the stationary phase. $nder these circumstances however gravitation is insufficient to drive the solvent through the system" so a pressure is used to drive the materials through the column. This process is called high,performance liquid chromatography" ?50!. The ?50! technique is used to separate mixtures and the components can then be analysed.

G(s>Li7+i* Chr)m(tr)'r(2hy
In gas,liquid chromatography the mobile phase is an inert gas and the stationary phase a liquid coating on a powdered inert solid. The powder fills a coiled tube which about &mm in diameter and up to %(m long. The coiled tube is situated in an oven which controls its temperature.

>+rin#e containin# samp(e

Fetector ,ecorder .o(9mn pac3ed with (iD9id coatin# on a powdered inert so(id -hermostatica((+ contro((ed oven

.arrier #as

The vaporiCed sample is in+ected into the carrier gas which moves through the tube at a constant rate. Dolatile components of a mixture are carried through the tube fast" while those that are more soluble in the mobile phase take longer to pass through the tube. The time a component spends going through the tube is called the rete%ti)% time. The area under each peak from the recorder is a measure of the amount of that component.

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