396 ANALYTICA CWIBIICA ACTA VOL.

7 (1952)

THE DISTINGUXSWING OF ORGANIC MATTER IN WATER

The determination of organic matter in water, indicating pollution, represents

the central problem of drinking water analysis. Many methods have been deve-
loped, almost all of them are based on the oxidation of organic matter. Potassium
permanganate, sodium hypochloritc and chloramine, as well as potassium dichro-
mate, have been recommended as oxidising agents. The basic methods are the
determination of oxygen consumed by potassium permanganate in acid medium
according to KU~EL AND TIEMANN~,the same determination in alkaline medium
according to SCHULZE AND TROBIMSDORPF~, the determination of “chlorine number’*
according to ~ROBOESE3, and the detection of fluorescence in ultraviolet light4,
In the oxidation methods mentioned, it is impossible to oxidize thoroughly
the organic matter in water, except when a very easily oxidizable matter is pre-
sent. The consumption of oxidant depends on its concentration, on the sort and
concentration of the substance in question. and on the duration of the test.
The amount of the consumption obtained experimentally represents always the
sum of various partial oxidations of various substances up to various degrees.
Thus, the consumption of oxygen indicates only that part of the respective organic
substance which is liable to oxidize under given conditions. In order to obtain
comparable results, the experimental conditions must be kept always the same
(Standard Methods).
Another important objection conccrn~ the fact that different concentrations
of various substances can consume the same quantity of oxidant even under
identical conditions. It is therefore impossible to conclude from a single determi-
nation whether a small amount of an easily oxidizable matter or a larger amount
of a sparingly oxidizable one was present in the test. This is, however, the clue
to the problem. Whilst a greater concentration of matter which is very sparingly
oxidizable indicates an older pollution, a smaller concentration of easily oxidi-
zable matter indicates a recent pollution.
In this paper a new method of the determination of oxygen consumption
in acid medium has been proposed, by which it is possible to obtain better infor-
I~cfLw9Kcs p. 4OI
VOL. 7 (rg$r) ORGANIC TbfATTER IN WATER 397

mation about the oxidizability and therefore to distinguish better the organic
matter in water. Several analogous experiments detemtining “chlorine number”
are also mentioned.

EXPERIMENTAL AND DISCUSSION

a. Determination of oxidizability by fiotassium @mmznganate

The experiments have been carried out according to the American Standard
Methods6: ro ml of 0.01 N KMnO, and IO ml of sulphuric acid (I: : 3) have been
added to IOO ml solution and heated in a boiling waterbath. The potassium per-
manganate consumption has been
determined as usual by adding
oxalic acid solution in excess and
by retitrating with potassium
permanganatc solution. The con-
sumption of KMnO, in redistilled
water has been determined simul-
taneously and the amount has
been subtracted from the test
consumption. Our experiments
have been carried out in the same
manner, but differing in the length
of time of oxidation. By the ori-
ginal method 30 minutes arc necd-
ed, whilst in our case the length
of time of oxidation was 15, 30
and Go (or rrzo) minutes respcc-
tivcly. Jn this way we obtained
three (or four) data instead of a
single one in the original proce-
dure, and so it was possible to
show the course of oxidation
graphically.
Time lfl Mlnutes
The following organic com-
Fig. f. Oxdatlou of dextrose, tyrosinc,
pounds were used : dextrose, gallic galfic acid, hlppurlc ncid and gclntxnc by
acid, tyrosine, hippuric acid, uric 0.01 dV potassium pcrmanganate (10 ml to
acid, aspartic acid and urea, as 100 ml solution}
well as undefined organic matter
like urine, sewage, gelatine and an aqueous extract of hay. Larger quantities of
some of the compounds mentioned occur in urine (urea 25-35 g, uric acid o.g-x.0 g,
hippuric acid 0.1-z g, dextrose about 0.5 g in about 1200-1500 ml of urine). The
concentrations of organic matter used in these experiments were chosen so tl\at
lt’cfcrences $. 401
398 H. IVIZKOVIC, A, GERTNER VOL. 7 (x9$?)

oxygen consumptions were about the same as those which are most often obtained
with polluted drinking water.
The oxidation curves for the above-mentioned organic compounds arc represen-
ted in the Figs. r-3. It follows from these diagrams that the oxidation process
with certain substances is
completed within the first 15
minutes and their oxidation
curves are therefore strongfy
convex at the beginning. On
the other hand other substan-
ces arc oxidized wcr a longer
period of time. Among the
examined compounds and mat-
ters which show a quicker
oxidizability may be included
dextrose, tyrosine, gallic acid
and fresh faecal material (diiu-
ted urine and sewage). Hip-
puric acid and gelatinc are
more slowly oxidized by potas-
sium permanganate under the

15 45 SO

F16. 2. CM&&ton of uric acid,

diluted urtnc and
a maccratc of hay by 0.01 h’ potassium perman-
ganate (x0 ml to 100 ml solution)

mentioned conditions. Uric acid belongs rather

to the class of readily oxidizable compounds
than to the opposite one. Urea is practically
unoxidizable. Its oxidation is thcrcforc not rep- $6 30 60
resented graphically. The longer the diluted Time in menu%
urine and the sewage were exposed to the air and FJg. 3. Oxidation of cil-
to the bacterial decomposition the flatter were lutccl scwagc by 0.01 h'
potasszum permanganate
their oxidation curves. (2s ml to zoo ml of d~l.
The more or less strong convexity of the oxi- sewage)
dation curves within the first 30 minutes corres-
ponds to the more or less easy oxidation of organic matter in water. The relation
of oxygen consumption within 15 and 30 minutes can be expressed numerically
lZcferc9tce.9p. lox
VOL. 7 (1952) ORGANIC MATTER IN WATER 399

as the quotient of oxygen consumptions in the mentioned periods of time. We

call this ratio the relalion of oxidizabilily (R.O.) :
p.p.m. oxygen consumed up to 30 minutes
= R.O. 30/x5 (IO) where the
p.p.m. oxygen consumed up to 15 minutes
number IO in brackets stands for the number of ml of 0.01 N KMnO, used in
the test.
The easier the oxidizability of organic matter in water, the more the relation
of oxidizability approaches I, showing more recent pollution.
Thus, e.g., with dextrose (5 and IO mg/l, resp.) the relation of oxidizability
30/15 (IO) was obtained as 1.1 and 1.0, resp., with gallic acid (5 mg/l) 1.0, with
tyrosine (5.4 mg/l) 1.1, with uric acid (11.7 and 25 mg/l resp.) 1.2 and 1.1, resp.,
with hippuric acid (IO and IOO mg/l, resp.) 2.0 and 1.5, resp., with aspartic acid
(30 mg/l) 1.4, with gelatine (20 and IOO mg/l, resp.) 1.4 and 1.8, resp. Fresh diluted
urine (2 ml/l) showed for the same relation of oxidizability a value of 1.1, after
7 days 1.6 and after 21 days 1.8. In the same manner, the numbers obtained
for diluted sewage were 1.1, 1.1 and 1.3. This proves that the R.O. is increased
by the bacteriological decomposition of organic matter in water.
These experiments have shown once more that the compounds rich in nitrogen,
especially urea, are extraordinarily resistant to potassium permanganate.
Further experiments were carried out using 2.5 and 5 times greater concen-
trations of KMnO, and longer period of oxidation time. The R.O. calculated from
the results of these experiments were approximately of the same values as the
R.O. mentioned previously.

b. Determination of oxidizability by sodium hypochlorite

Several analogous experiments determining “chlorine number” by the arsenite

method0 were also carried out. Four characteristic substances were used: dextrose,
hippuric acid, urea and diluted urine. The concentration of the oxidant was kept
constant: 20 ml of 0.02 N NaClO per IOO ml of the examined solutions.
From Fig. 4 it can be seen that each of the four substances can be, more or
less, oxidized by sodium hypochlorite in alkaline medium under the usual conditions
(boiling waterbath).
The relation of oxidizability 30/x5 obtained by hypochlorite was for dextrose
(IO and 50 mg/l, resp.) 1.3 and 1.10, resp., for hippuric acid (I, IO and 50 mg/l,
resp.) 1.4, 1.5 and 2.5, resp., for urea (IO and 50 mg/l, resp.) 1.10 and 1.0, resp.,
for urine (0.04, 0.4 and 2 ml/l, resp.) 1.3, 1.0 and 1.0, resp. These numbers-ana-
logous to those obtained by potassium permanganate - prove that the hippuric
acid is a sparingly oxidizable matter, whilst the other matters, which were used,
are more easily oxidizable. In contrast to the resistance of urea to the oxidation
by KMnO, this substance is easily decomposed by hypochlorite.
References p. qor
400 H. IVEKOVIC, A. CERTNER VOL. 7 (x952)

Furthermore, the relations of oxygen consumed within 15 and 30 minutes,

respectively, by sodium hypochlorite and by potassium permanganate

p.p.m. oxygen consumed by NaClO

p.p.m. oxygen consumed by KMnO,

for the same concentrations of organ-

ic substances, have been also com-
puted. For this relation we obtained
with dextrose (IO m&l) the value
4.3 : 4.6 = 0.9 and 5.6 : 4.9 = 1.1,
for hippuric acid (IO mg/l) 2.0 : 0.2
= x0.0 and 3.x:0.4= 7.7, for diluted
urine (z ml/l) 28.4 : 5.6 = 5.0 and
28.4 : 6.5 = 4.3. For urea this rela-
tion is naturally extremely high.
These experiments confirm again a
well-known fact, i.e., that in sub-
stances rich in nitrogen this relation
is considerably higher than I, indi-
cating very often a fresh organic
matter of faecal origin’.

SUMMARY

A method for the distinguishing /U&e

of organic matter in water has been
proposed. The method consists of the
determination of oxygen consumed ~---D~;t roseWa$I~
by potassium permanganate or by r=llc 1 Hippurlc Acid(lmq/l)
sodium hypochlorlto in the time in- V I
tcrvals of x5, 30 and Go (or 120) 15 60
minutes respectively, from which it IS
possrble to plot the curverepresenting
the oxidation velocity. The oxidiza- Big. 4, Oxidation of dextrose, hippuric acid
bility of organic matter in water may and diluted urine by 0.02 N sod&urn hypo-
be express& numeri+ly by the ratio chlorite (25 ml to IOO ml solution)
of oxygen consumed within 30 and
13 minutes or within Go and 30, respectively (relation of oxidiznbility). The quicker
the oxidation of organic matter takes place, the more the relation of oxiditability
approaches the value of I, thus indicating a recent pollution.

Les ZL~L;;X proposent une mdthode de dosage de matieres organiques dans

I’eau
Cet Pe m&ode consiste tlr doser le permanganate ou l’h ochlorite de sodium
en excb apres IS, 30 et 60 (ou x 20) minutes, On peut ainsi &a tsp
lir la courbe de vitesse
d’oxydation.
References p, gor
VOL. 7 (1952) ORGANIC MATTER IN WATER 401

L’oxydabilite des mati&res organiques dans l’cau peut s’exprimcr par la relation
de la quantite d’oxygene consommee pendant 30 ct 15 minutes ou 60 et 30 minutes
respectlvement (rapport d’oxydabilite). Une pollution rccentc donnc une valeur
qui s’approchc de 1.

ZUSXMMENFASSUNG

Die Vcrfnsser beschrelben tine Methodc zur Bestimmung organischcr Substanz

im \Vasser. Hierbci wird der Ubcrschuss an Permanganat oder Hypochlorit nach
15, 30 und 60 (odcr 120) Mmutcn bestimmt und die Kurve der Oxyclatrons-Ge-
schwindigkcit gczeichnet.
Die Oxydlcrbarkeit organischcr Stoffe kann durch das Verhaltnis dcr wahrend 30
und 15 Minuten (oder Go und 30 Minutcn) verbrauchtcn Sauerstoffmengc ausgcdruckt
werden (Oxydierbarkeltsverhaltnls).
Fur einc frischc Verunrelnigung nahcrt sich dlcscr \Vcrt dcm \L’crtc I.

REIXRENCES

f OrrnxtiLLEr+Srl-rr,\, ~~zicvs. u?rd Beuvtclluq tics fVnsscrs zwd .~~.!~x~asscrs. Dcrlln,

1931.
a H. TROnlnISDORTF. z. allal. Cfrery.. 8 (1869) 344.
3 V. FROBOESE, ArDczt. aus d. I~eachsgcsrc?r3/rcltsci),rt,52 (rgzo) 211.
4 H. IVCKOVIC, Z. I-Iyg. 16. I?zfclrl. itvanklb., I 12 (x93x) 54.
6 ARTY. Stawiavd Methods fey the E.vanzl?ration of CVntcv alzrl Scrmgc. 9th Ed. Am.
Publ. Health Assoc., N.Y., 1946.
8 H. Ivelcov~d, Z. anal. Chew.. 103 (1935) 138.
7 H. HALC. M. SULIVANT AND CII. Dc 1\‘irr, J. Arjz. IVatcv Il’o~lts ,Assoc., 20 (1928)
846. - A. IhESS, /1YC/b. lly&?.. IO7 (1931) 42. - I-1.IVlXOVlC, /IY/bZU /-lCUb.
Technol., 8 (1934) 185, 12 (1938) 118. - RI. GIBSON, Analyst, 67 (1942) 125.

Received May x3th, 1952