376 
DR. MEYER AYTLHERMAN ON CHEMICAL DYNAMICS 
If we now draw curves, taking the times t s as abscissae and the corresponding 
i // 
7T — 7T 
amount of carbonyl chloride formed (i.e., the 7r’s) as ordinates, then the - - ’s or 
r 2 ~ T 1 
cItt 
- ’s give the rate of formation of carbonyl chloride, or the rate of combination of 
dr ^ J 
chlorine and carbon monoxide. The curves appear to be remarkably regular, especially 
those obtained with the glass bulb. The total number of direct observations is in 
Table I. about 70. To trace the nature of the curve through its whole length 
observations were made at small intervals, thus dispensing with interpolating results. 
Errors arising from the variations of the temperature of the bath, from the variations 
of the barometric pressure, &c., can never be completely eliminated by the application 
of corrections. For this reason they are greater in the results obtained for small 
intervals than when greater ones are taken. By this method the phenomenon is 
nevertheless more thoroughly known and its nature more evident, since such an 
investigation of the curve does not permit of phenomena characteristic of only one part 
of the curve obscuring the true nature of other parts of the curve. As will be seen 
from the tables given below this course proved to be necessary in our case, since at 
the beginning of the curves we always met with a peculiar phenomenon, called 
“ induction,” not characteristic of the rest of the curve. 
dir, 
When the 
7r 
7r 
To — t , dr 
s or — ’s are successively taken on the curve and compared with 
one another, we find that they start with very small values approaching zero (the 
curve starts asymptotically to the abscissa), and gradually increase till they reach 
a maximum, after which they gradually decrease. If we consider curves (l), (2), (3), 
(4) and (5) of Table 1. as parts of the same curve, belonging all to one system, we find 
dir 
that the — ’s gradually diminish, approaching the value of zero, i.e., when no more 
(IT 
reaction takes place. This takes place when one of the combining substances com¬ 
pletely disappears from the gas mixture. 
• . dir • . • 
An investigation of the curves, after the — ’s arrived almost at their maximum, 
° dr 
shows with absolute certainty that the equation 
[log, (A — aq) — log, (A — x 2 ) -f log, (B — x. 2 ) — log, (B — aq)] : (r . 2 — iq) = C (l) 
(a constant) holds good, where A and B are the quantities or volumes or partial 
pressures of chlorine and carbon monoxide before the reaction was first started, 
expressed in millimetre pressure of the manometer. A — aq, A — aq, B — aq, B — aq, 
are the quantities of chlorine and of carbon monoxide present in the system at the 
times t : and r 2 (see Table II. below). 
It is thus evident that our integral equation must be 
JZTb P°& ( A ~ ~ lo & ( A _ x i) + lo & ( B — x i) - lo g‘- ( B - *])] : ( t 2 - b) = K (2). 
