A h rh e cJ ( 3 }

Unit 6 chem istry

Flome tests - Procedure:

■ First the te st sam ple is converted into a chloride sa lt by adding concentrated HCI acid. This is because chloride salts are m ore
volatile than any other com pounds and hence som e of the unknown goes into the gas phase readily when heated in the hot non-

lum inous part of flame.

• Platinum o r nichrom e wire is chosen because they have high heat conductivity and unreactive in the flam e. The wire is cleaned by
dipping it in som e concentrated HCI acid on a watch glass and then placing it in the h ottest part (blue part) of a Bunsen flame.
Once again, the clean wire is dipped in concentrated HCI acid and then som e of the solid under test.
This is then placed in the hottest part (blue part) of the flam e and the colour of the flam e is observed.
P rD rf(} o rf
Flam e colour Inference
* A d d Cooc. fo ft>i? SJfrpi*? Yellow Sodium ion, N a +

Lilac Potassium ion, K*

* 0 )(° P i Or Ni(hror«? wirt?
Yellow -red / brick red* Calcium ion, Ca2+ U e o n ^ b r ^ r m m e
in §or-<? (cm . HCI b cte>i d
t ie * cvev k jn s 'C K h o fin ? 1' Crim son red* Lithium ion, Li+
Carm ine red* Strontium ion, S r2*
. 0 'p i f ]r‘ 1 ^ Pale / apple green Barium ion, Ba2*
it e r ■ fU 5 , pY
Blue Copper (II) ion, Cu2+

* p ljie >
v * No colour Magnesium ion, Mg2+

O rigi^ o f Flame Colour: The heat energy of^tie flame causes the compound to vaporize and prom otes an electron in^he m etal ion
into a higher energy level or e xcite ^ sta te . T heelectron falls back to its normal shell o r ground ^Ipte and as it does so ,'e n e rg y in the
form of visible light is emitted. T h e u g h t that is emitted of a characteristic frequency, and hence colour, is dependent on the en ergy
level difference between the two shells.

The unknowns that you could be asked to identify are:

alkenes alcohols I halogenoalkanes I aldehydes and ketones 1 carboxylic acids ca rb o x ylic acid d e riv a tiv e s

T est F o r *H OBSERVATION Inferences

Burn a few drops on a crucible lid It burns with a clear non-smoky flam e Low carbon to hydrogen ratio
It burns with a sm oky flame High carbon to hydrogen ratio

S olu bility in w ater and pH test

Test OBSERVATION Inferences

Add to water ■ Either two layers form • Either no OH group; or if an alcohol o r acid it has a high m olar m ass
■ Or it dissolves fully (at least four carbon atom s)
■ Forms hydrogen bonds with w ater, so has an OH group
Add litm us ■ Litm us paper (o r Ul solution)goes red ■ it is an acid
o r universal • U l solution goes green ■ it is a neutral substance (not an acid)
indicator (Ul)

* b r o ^ n b*-err» « '* — > ( £ Iq i v ' & S

Test OBSERVATION Inferences
Add som e bromine water to the orange brom ine w ater goes colourless and two layers are form ed C = C group present
unknown - stopper the test Brown brom ine qoes colourless
Add acidified KMn 04 Purple colour becom es colourless P \ jfP \ g . — C= C group present
Add alkaline KM n0 4 Purple colour disappears and form s brown ppt —:> -f- C= C group present

Tests for halogenoalkanes

Test
O BSERVATION Inferences
Shake a few drops of the unknown with w ater
Two layers form
Add a few drops of ethanol and aqueous silve r nitrate and dilute n itric acid - W hite precipitate It contains a C-CI group
stand the test tube in a beaker of hot water
C ream precipitate It contains a C -B r group

H ^ C 2, ^ ) 1^ i U ) ? r rv^
 Yellow precipitate It contains a C-l group-^
W hite precipitate It contains a C-CI groupJ
Add 4 drops of ethanol and then 2 ern^of dilute sodium hydroxide - stand the
Cream precipitate It contains a C -B r group
test tube in a beaker of hot water for 5 m inutes: then add excess nitric acid
Yellow precipitate It contains a C-l group
followed by aqueous silve r nitrate | +* & (^z)
Add concentrated sodium hydroxide in ethanol - fit the test tube with a delivery orange brom ine w ater H -halogen elim inated

tube and warm gently, passing any gas evolved through a little bromine water goes colourless form ing an alkene

A /rO H /fo r/) 1 (rthfirfi I i d fluO rY i lo^>rn -V cJ ^ i Pi-pUtfd *•*> &

The identity of the halogen in the precipitate formed with silver nitrate can be confirm ed by adding am m onia solution.
Observation Inferences
Precipitate dissolves in dilu te am m onia The unknown is a chloroalkane

Precipitate insoluble in dilute but soluble in concentrated ammonia The unknown is a brom oalkane
Precipitate insoluble in concentrated am m onia The unknown is an iodoalkane

T est for aldehydes and ketones, These contain the C=0 group.
Test OBSERVATION Inferences
Add a few drops of a solution of 2,4-dinitrophenylhydrazine A yellow or orange precipitate It is an aldehyde or a ketone

T e st to distinguish between an aldehyde and a ketone

Test OBSERVATION Inferences

Add a few drops of the unknown Either red precipitate it is an aldehyde
to som e Fehling's (or Benedict's) solution and warm Or the blue colour remains it is a ketone
Add a few drops of the unknown to Tollens' reagent Either silver mirror formed It is an aldehyde
and w arm Or solution stays colourless It is a ketone*
Add a few drops of the unknown to acidified Either orange solution goes green It is an aldehyde*
potassium dichrom ate(vi) i solution 7" Or solution stays orange It is a ketone*
Add a few drops of the unknown to acidified Either purple solution decolourised It is an aldehyde
potassium m anganate(vii) solution and warm Or solution stays purple It is a ketone

Tollens* reagent is m ade by adding aqueous sodium hydroxide drop by drop to aqueous silver nitrate until a grey precipitate is
form ed. The clear liquid above the precipitate (the supernatant liquid) is poured off and the precipitate dissolved in the minim um of
dilu te am m onia ~ /M J fe v V \ ----- A ,'. W/0 -, I - A oJre vrpV f e w , — •> PfHI X c -U d
• rtPr^ovrO ^ *0
To & ^ The iodoform test - This iis a reaction between an alcohol or carbonyl compound and a solution of iodine and sodium hydroxide.
— ------------------ Oh-
The m ixture is then allowed to stand. It is a ketone* The formula of iodoform is CHI3. It is a pale yellow solid that is insoluble in

w ater. It has an antiseptic sm ell. Iodoform is produced when an organic compound containing the CH 3C =0 (Methyl ketones) or
CH 3CH(OH) group is gently warm ed with iodine mixed with sodium hydroxide solution. The only aldehyde that performs the iodoform

reaction is ethanal. The equation for the reaction of butanone is:

o
CHi C0C2Hs 1 31? t 4NaOH » C2H5COONa h 3NaI t 3HZ0 , . fl
- C - c - '1 ' f ( * *’
Alcohols undergo th is reaction if they can be oxidised to give rise to’ a C H jc = 0 (Methyl ketones) group. Ethanol is the only primary
alcohol th at gives a precipitate of iodoform . The alkaline solution of iodine oxidises it to ethanal, which then reacts to give the
precipitate:
The sequence is: ethanol" -» ethanal -* iodoform + sodium methanoate

2
O bservation Previous test Inferences
Pale yellow ■ A precipitate with 2 ,4-dinitrophenylhydrazine - showing it to be a It contains a C H 3C = 0 group
p re cipita te (of carbonyl com pound
iodoform *) ■ A red pre cipita te with Fehling's (or Benedict's) solution or ■ it is ethanal
(triiodom ethane) ■ a silve r m irro r with Tollens' reagent - showing it to be an aldehyde

• S team y fum es with PCI5 or other test - showing it to be an alcohol ■ it contains the H 3CH(OH)group,

for exam ple propan- 2-ol

T ests fo r OH group in alcohols and carboxylic acids

T e st OBSERVATION Inferences

Add a sm a ll piece of sodium to the Bubbles evolved It contains an OH group and so is an

unknow n in an evaporating basin Sodium disappears or a white solid form s alcohol, phenol or a carboxylic acid

(T & f/c t' - C H $ rc v p )

Add solid phosphorus(V) chloride p £ j^ jd S team y fumes evolved It contains an OH group and so is an

and test any gas evolved: alcohol o r a carboxylic acid

e ith e r with a glass rod dipped in W hite sm oke formed

r io t p h e n o l
concentrated ammonia;
o r with dam p blue litm us paper Litm us goes red

T o distinguish an acid from an alcohol

T est OBSERVATION Inferences

Add the unknown to a solution of sodium Fizzing It is a carboxylic acid

carbonate or sodium hydrogencarbonate Gas evolved turns lim ew ater

and test any gas evolved with lim ew ater cloudy

Add blue litm us (o r universal indicator) to a solution of the unknown Litmus goes red It is a carboxylic acid

Add som e ethanol (or other alcohol) and a few drops of concentrated Fizzing It is a carboxylic acid (and

sulfuric acid to the unknown and warm. Then pour into a beaker an e ster is form ed)

containing some sodium carbonate solution and cautiously sm ell the Sm ells of glue/fruity sm ell

product /ik p ta p l -b - CU—?r- - - — > A/ ^ ^3

RCOOtf + NaHCOj - 4 RCOONa + H20 4 C02 C02 •» Ca(0H)2 -> CaCO, + H20
2RCOOII 4 Na2C03 -4 2RC00Na 4 H?0 4 C02 ^

T ests for acid chlorides j <^£^1 C ^ A p ) r iC \ c f _____________________________

T e st ' Observation
Add the unknown to som e water in a test tube, Then add dilute nitric acid and aqueous silv e r nitrate S te am y fumes
W .-afev' -h M A O .ild il) +- i( 3 & ) W hite precipitate
Add the unknown to som e ethanol and th e n p o u r into a beaker containing aqueous sodium carbonate. Fruity/glue sm ell
Carefully smell the beaker's contents P r U A V ’O l

A re n e s - A ro m a tic com pounds burn w ith a sm o k y flam e. Phenol and p jie n yla m in e ra p id ly turn b ro m in e w a te r from brow n to
co lo u rle ss, with th e form atio n of a w h ite p re cip ita te , for e xa m p le : a / - 3 £ o j 0i/ y ) c #

3
 C o n iv r 'W f\cA ' v/- .1 ,J 3 c . a
|f(;n c f r
_> — > /V a d
Laboratory preparation of phenylamlnc
' <rir>-»i*oc _____________

0 CftHsNO? and Sn are mixed In a round - bottomed flask fitted

with 0 reflux condenser.
n IS
t-r 'i/
c 'i'' c t h U'i
0 Concentrated MCI Is carefully added then the m ixture Is / d '*>Ml
w ater out
heated to 100°C in a water bath for 30 minutes.
concentrated
a M ixture Is cooled room tem perature, the condenser removed hydrochloric a cid
and an excess of NaOH Is carefully added with cooling.
/ J ) y<\\
w ater In
0 Finally, the m ixture is steam distilled by blowing steam onto a p f
the m ixture and condensing the phenylam lne, which is then
placed in a separating funnel with sodium chloride to reduce
the solubility and the phenylam lne layer is run off and dried
with potassium carbonate to rem ove water. r
c o ld w ater w h ile adding
nitrobenzene <* the acid, th e n b oilin g to
0 The C 6H 5NH 2 Is decanted off from the solid K 2CO j and
w c o m p le te the reaction
distilled. It Is then distilled using an a ir condenser. tin
____ J

Benzenediazonlum com pounds - Laboratory preparation ^ CCo\

• Phenylamlne and hydrochloric acid are mixed and the m ixture Is cooled to 0°C in an Ice bath.
■ A solution of N aN 02 (cooled to 0°c) is slowly added, making sure that the tem perature neith er rises above 10°C n or falls below
0°C.
■ The solution is kept at 5°C and used as necessary,

Coupling reactions of dia zonium Ions - Arene diazonium ions are weak electrophiles; they react with h ighly re a ctive a rom atic
com pounds—with phenols ancf tertiary arylam lnes—to yield azo compounds. This electrophilic a rom atic substitution is often ca lled a
diazo coupling reaction.

Reaction with phenol Reaction with phenylam ine

Yellow ppt
*»;0
f Y NHj
< ^ - N E N CP + + HO
Baizcncdiazonium Plicnol />•!lydrcrt)azobetittnc
chloride (Orange dye) P c > l&

t l

A
reaction mixture
after refluxing \r< i

heat
ethano1 and pure
ethenofc a cid with
concentrated im pure
p ro d u ct

organic layer g ra n u '« c f

frcm separating c a lciu m ch lo rid e shake w ith so d ium carb onate
funnel (a dryin g agent) so lu tio n run off aq ueo us layer,
then shaken the ester w ith CaCI2
so lu tio n to remove unchanged
ethano*

4
NMR spectra
The points to look for are:

T h e num ber o f peaks - th is g iv e s th e num ber of different environm ents of th e hydrogen atom s. For exam ple, propan-2-ol,

C H 3CH (O H )C H 3# will have th ree peaks because the hydrogen atom s in both C H 3 groups are in the sam e environm ent.

P ro p a n -l-o l, C H 3CH 2C H 2OH, will have four peaks.

• T h e splittin g pattern - if a peak is not split, eith er the group has no hydrogen atom s on adjacent carbon atom s (as in
propanone) o r it is next to an O-H group:
- If it is s p lit into 2 there is one hydrogen atom on the adjacent carbon atom
- If it is s p lit into 3 then th ere are tw o hydrogen atom s on adjacent carbon atoms
- If it is s p lit into 4 then th ere are three hydrogen atom s on adjacent carbon atom s
• T he chem ical shift, 6 ppm - the H of the 0 -H in alcohols has a d between 2 and 4 ppm:
- In ca rb o x ylic acid s between I I and 12 ppm

- In C H 3, C H 2 or CH between 0.5 and 3.5 ppm

You will be given tw o or three d-block com pounds as solids or as their solutions. Cations
The ca tio n s will be lim ited to Cr3*, Mn2\ Fe2\ Fe3\ C o2*, Ni2*, Cu2> and Zn 2*; and possibly K +, Na* and N H 4 \

A pp earance of solid Appearance of dilute s o l u t i o n ______________________ _

r-------- - ~
j Colour Possible ions 1Colour Possible ions
j Colourless Zn2< 1 Colourless Zn3\ Mn2'
l 1
' Green Fe2\ Cr»*.Ni2\ Cu2" j Green FeJ'.C r , \ N i2*

|Blue Cu2f j Blue Cu*~

j Pink Co2\ Mn2* ( Pink Co**

r
t Orange Cr20 ,’ - |Orange CrjO;2
] Yellow CrO«2 j Yellow CrO,1
j Purple MnO," j Purple MnO<

h»* *•»*

Colour in Violet Very pole pirfc Pole blue green Yellow Emerald green Blue
aqu^oirt
solution

Anions - The anions will be lim ited to S 042*, SO32', Cl*, Br', I', NO3 and CO32'; plus C r 0 42' , C r 20 72 and M n 0 4 .

The anions that show effervescence with dilute acids are SO32 and C 0 32*
Reasons for adding dilute HCI in sulfate te st (not sulfuric a c id .......................... -.....................................................
Reasons for adding dilute nitric acid (not sulfuric acid, HCI)......................................................................................
 O bservations In feren ces
Test
tC ^ A gas is produced which tu rn s lim ew a te r It is a carbonate
Carbonate - Heat the solid - test any gas evolved with
cloudy
lim ew ater
Bubbles / (or fizzing or effervescen ce) It is a carbonate
Acid * solid -test any gas evolved with
Lim ew ater turns m ilky cloudy
Lim ewater
W hite precipitate turning purple on it is a ch lo ride
Halide - Add dilute nitric acid to a solution of the
unknown and then silver nitrate, Ju st the precipitate: standing soluble in dilu te am m onia
Cream precipitate insoluble in d ilu te it is a brom ide
first with dilute am m onia and then (if no change) with
but soluble in concentrated am m onia
concentrated am m onia fy N O j
Yellow precipitate insoluble in it is an iodide

concentrated am m onia

Nitrate - Add Devarda's alloy (or alum inium powder) and • Bubbles(effervescence) it is a nitrate

dilute sodium hydroxide and warm - test any gas evolved: ■ W hite sm oke
either with a glass rod dipped in concentrated hydrochloric • Litm us goes blue
acid or with dam p red litm us rn
Sulfate - A few drops of dilute hydrochloric acid are White precipitate which stays on B a 2*(aq) + SO „ 2'(aq)

added to the unknown solution followed by a few drops of addition of hydrochloric acid. B a S 0 4(s)
barium chloride solution. Som etim es the barium chloride
is added first, followed by the hydrochloric acid. f QoC\
Sulfite - A few drops of dilute hydrochloric acid test any ' "The colour of acidified potassium s u lfu r dio xid e evolved on
gas evolved: with acidified potassium dichrom ate(vi) dichrom ate changes from orange to w arm ing which is a

liV - ^ g A —b K 362O 7 9 reen colourless, acidic gas

:V /o W

Addition of sodium hydroxide until in excess /

Ion OBSERVATION a f t e r a l i t t l e N a O H a d d e d O b s e r v a t io n s a ft e r e x c e s s

Fe2* Green precipitate which goes brown on standing Precipitate stays

Fe3* Reddish brown ppt Ppt stays
Cr3* Green precipitate Forms green solution
Ni2* Green precipitate Precipitate stays
Cu2* Blue precipitate Precipitate stays
Mn2* Off-white (buff or sandy) precipitate which darkens on standing Precipitate stays
Co2* Blue precipitate which goes pink on standing Precipitate stays
Z n 2* White precipitate Forms colourless solution

Addition of ammonia until in excess

Ion O b s e r v a t io n s a ft e r a lit t le N H 3 a d d e d O b s e r v a t io n s a ft e r e x c e s s

Fe2* Green precipitate which goes brown on standing Precipitate stays

Fe3* Reddish brown ppt Precipitate stays
Cr3* Green precipitate Precipitate slowly dissolves in concentrated ammonia to
form green solution
Ni2* Green precipitate Forms blue solution
Cu2* Blue precipitate Precipitate dissolves to form a dark blue solution
Mn2* Off-white (buff or sandy) precipitate which darkens on standing Precipitate stays
Co2* Blue precipitate which goes pink on standing Precipitate Slow ly dissolves to form a brown solution
Zn2* White precipitate Forms colourless solution

6
 Transition metal ions in hydrochloric acid

Ion Oil HCI Cone. HCI

C r 34 Green solution Green solution

Mn 24 Colourless solution Colourless solution

Fe1* Green solution Green solution

Fe 34 Colourless solution Brown solution

C o 24 Colourless solution Dark blue solution

Cu** Green solution Yellow solution

Ni 24 Blue solution Yellow brown solution

Ag4 W hite ppt White ppt

Z n 24 Colourless solution Colourless solution

Oxidation State
+2 +3

-041V \ H .V .V
Acidic Cr‘ +(i7ip -------- Cr ------- * Cr<>7* (ay)
A n ja >oIulion: Chromium(II) ton Chromium(III) ion Dichromale ion
14 C \ (Chromous ion) (Chromic ion) Orange
Blue Violet
- 0.1? V
Haste CrfOH)'(s) Cr(OHV$) *------- Cr04:“(*j)
A r") solution: Light Blue Pale Given Chromate ion
Yellow
CtfOH)4
Chromite ion
Deep green

Vanadium - Vanadium form s stable compounds in 4 different oxidation states, +2, +3, +4 and +5. In aqueous solution, the ions
formed are:

Oxidation state +5 +4 +3 +2
Colour yellow Blue qreen Violet
Ion v o 24 VO24 V 3* V 24
All vanadium (V) com pounds can be reduced to the +4, +3 and then +2 oxidation state by strong reducing agents such
as zinc in acid solution:
KJ
Redox tests - Addition^of potassium iodide - Aqueous potassium iodide is added to a solution containing the unknown ions, which
oxidise the io d i^ ions to iodine. Starch solution is then added.
Ion Observation Starch added
Fe3+ Red-brown solution Blue-black colour
Cu2* Red-brown colour with precipitate Blue-black colour
Cr 20 72' or C r0 42' in acid Brown colour Blue-black colour

Addition of aqueous chlorine (chlorine water) - This is a redox reaction in which chlorine oxidises the unknown ion

Ion Observation
Br- Red colour
I- Red-brown solution Goes blue-black when starch added
Fe2* Goes slightly brown The Fe3* ions can then be tested using NaOH

7
Addition of other oxidising agents

O bservation s with lead(v) oxide as the

Ion to which an oxidizing agent is
added
C r3* in alkaline solution
Fe2+in acid solution
O bservation with hydrogen peroxide as the
oxidising a gent follow ed by filtration
oxidizing agent
Yellow solution (o f C K V
Yellow solution of C r0 42
Goes slig h tly brow n, th e Fe 3* ions can
Goes slightly brown the Fe3* ions can then be
then be tested using NaO H(aq)
tested using NaOH(aq)

Observation on adding HjOj Inference

green precipitate turns brown iron(ll) hydroxide to iron(lll) hydroxide

green alkaline solution goes yellow chromium(lll) to chromate(Vlj

brown solution or black precipitate iodine from iodide in acid solution

brown pre cip ita te in alkaline lead (II); brown precipitate is Pb02
-solution_______

Deduction of order of reaction

There are four distinct m ethods that can be used to determ ine the order with respect to a reactant:
From initial rates From half lives From the slopes of a From the slope of rate-
concentration -tim e graph concentration graph
prom thejnjtial rates - The reaction rate changes throughout the reaction, as does the concentration of reactants and products, so
it is m ost accurate for com paring the initial rates of different reactions. In this method, the concentration of each reactant is altered
in turn to see what effect the change has on th e rate at the start of the reaction. The start of the reaction is chosen because th is is
the only point in the reaction at which the concentrations of the reactants are definitely known. Consider a reaction;

A + B + C -♦ products

The experim ental method is as follows:

❖ The initial rate is measured when all 3 reactants have the same concentration, for example, l.O O m oldm '3. This is at zero tim e.
❖ The experim ent is repeated with (A) =2.0 m oldm-3, (B) and (C) unchanged (1.0 m oldnr3)
• If the rate does not alter, the reaction is zero order with respect to substance A. this means that 'A' is not involved in RDS.
• If the rate doubles, it is first order in A.
• If the rate increases by a factor o f 4 it is 2nd order in A.
• A 3rd experim ent performed with (A) and (C) equal to 1.0 moldm 3 and (B)= 2 moldm-3. This enables the partial order with
respect to B to be deduced.
• A 4th experim ent is carried out In which (C) is altered but (A) and (B) are kept the same as in one of the previous experim ent.
This enables the order with respect to C to be deduced.

From half- lives - The second method involves monitoring the reaction throughout its course. In this procedure, the am ount of a
reactant o r product is established at various tim e intervals throughout the course of the reaction. For a first order reaction, the half-
life is co n sta n tto within experim ental error.

From th e slope o f a concentration - time graph - The reaction proceeds quickly at the start and slows down towards the finish.
The rate o f the reaction is fastest where the curve is steepest and the slope then decreases until the curve becomes horizontal,
which indicates that the reaction is complete. To provide a numerical value for the rate, the steepness of the curve is established by
finding its gradient. This is achieved by drawing a tangent to the curve. In the graph below, tangents have been drawn at two points
on the graph. The numerical values of their gradients show how much the reactions has slowed down from the initial rate (the
gradient at the start of the reaction 0 to a point about halfway through the reaction.

Form of graphs - When a graph of [A] is plotted against time, the shape of the graph depends on the order of reaction. The slope
of the graph at any value of [A] is the rate of reaction at that concentration.

DRAWING TANGENTS - The rate of any particular concentration can be calculated by drawing a tangent to the curve at that point
and measure the slope of the tangent. The slope of the tangent equals the rate of reaction

Example: Find the rate at 0.25 moldm 3 concentration of [A]. Initial rate=+0.17 moldm-3m in -1
8