TRANSFORMATION OF NITROAMINES AND ALLIED SUBSTANCES. 139 
Tasce II. 
| Acid : wee Percentage of Chloroamine converted into : 
es : {—— -—- (a) CY (b)CY + C10," (ce) Chloroanilide 
| HC1(2 mols.) . | 25° 54:24 8-12 37-64. 
| H,SO, (1 mol.) | 3 68-77 12-74 18-52 
| H,SO, (4 mols.) | os 65-39 15-46 19-14 
| HNO, (1 mol.) | ‘ 76-56 5-59 17-85 
(COOH), (1 mol.) oe 74:36 — 25-64 
HCl (10 mols.) be 12-2 — 87-78 
HCl (20 mols.) | m 7:73 — 92-28 
| HCl (4 mols.) . 60° 25-42 3-93 70-65 
| HCl (10 mols.) 60° 11-47 — 88-54 
HCl (2 mols.) . 585° | 43-76 9-36 46-98 : 
_ Water isis 60° | 63-59 — 36-42 
HSO, (1 mol.) | 60° 60-85 12-19 26-96 
_ H,SO, (10 mols. | 60° | 73-86 0-91 25-23 | 
The times which the reaction occupies in various cases are very different. 
The chlorination of the anilide is in an aqueous medium an extremely rapid 
reaction (Orton and Jones, Joc. cit.), and hence in circumstances when 
chlorine and anilide are present at relatively high concentrations, the 
chloroamine rapidly disappears, and a large proportion of chloroanilide is 
formed. This condition is realised when the concentration of the hydrogen 
chloride is sufficiently raised, for, as was shown in the foregoing, the hypo- 
chlorous acid is then replaced by chlorine: H’+ Cl’ + HClO — Cl,+H.0, 
and further hydrolysis of the chloroamine follows from disturbance of the 
equilibrium: Ar. NCl.Ac+ H,O +Ar.NH.Ac-+ HCIO. 
The time of the half-change in a number of the experiments is shown in 
Table III. 
Tasce III. 
| Experiment Acid | Heuer Half-period | pe raee Re 
i HCl (2 mols.) | 25° | 16-75 days 37-64 
ii | HCl (2 mols.) 60° 8-2 hours 43-6 
eal iii HCl (4 mols.) 60° 2-8 hours 70-65 
iv - HCl (10 mols.) 60° 40-5 mins. 88-54 
| v H,.SO, (1 mol.) 25° 31-5 days 18-52 
vi _ H,SO, (4 mols.) 25° 11-3 days 19-14 
vii | _H,SO, (1 mol.) 60° 18-7 hours 26-96 
viii | 4-9 hours 25-23 
HSO, (10 mols.) | 60° 
(i) A comparison of the experiments in which hydrogen chloride was 
used with that in which sulphuric acid was used at equivalent concentra- 
tion (i with v and ii with vii), whether at 25° or 60°, shows that with 
double the production of chloroanilide, the speed of the disappearance of 
chloroamine is also approximately doubled. 
(ui) With increase in the concentration of the hydrogen chloride, the 
Seen of chloroanilide rapidly increases. Raising the proportion of 
ydrogen chloride from 10 to 20 mols., roughly quadruples the speed, but 
only slightly raises the proportion of chloroanilide (from 88 to 92 per cent.). 
(iii) Increase in the concentration of the sulphuric acid is accompanied 
by an increase in the rate of disappearance of the chloroamine. But in 
marked contrast to the effect of hydrogen chloride, the reaction is still 
