mfety in the
MALCOLM M. RENFREW
chemkol loboratory
Risk Assessment and Hazard Elimination for
Undergraduate Laboratory Experiments
Jay A. Young
Chemical Consultant, 12916 Allerton Lane, Silver Spring, MD 20904
W r h perhapsafeu~rxeeptlons,allrheml-
cah have prupenwr that ran make the uqe of
there chrm~calshuarduus. For almost all uf
these, however, it is possible to take precau-
tions in their use so as to prevent any haz-
ardous properties from causing harm.
Examples of precautionary actions easily
come to mind. For examole. no knowledee-
~~ ~
able chemist would eve; add conrcntra;ed
perchloric acid to sugar errept in wry small
amounts under conditions that would divert
the certain explosive forces in a direction
away from persons and property.
is
Jay A. Vovng a chemical urnsultant
soecializina in the safe manufacture. use.
pecaulonary faceling, Moper hand1 ng. and
apprapr ate d sposar of chemicals ~ s e din
mdustry, the hoLseholo, and me laoaatay.
He writes articles and bwks, and organizes
and participates as a contributor to confer-
ences, seminars. and symposia in these
areas. He deDOSeS and/or testifies as an
exoert
- F~ . ~laintifl
witness lfar . or defense1 in
lot gat ons mrolv ng cnem cals or chemical
reactions an0 product haot ry. rle s Ed,ror
of the lntemational Journal of Chemical
Health and Safety.
The precautions to he taken in the use of
chemicals with hazardous properties are
typically delineated on the labels of con-
tainers of such chemicals. The principles
governing the preparation of precautionary
labels are found in "ANSI 2129.1-1976"
(1).
According to ANSI 2129.1-1976, alabel is
prepared by first identifying the hazardous
properties of the chemical to belabeled, and
then deducing all reasonably forseeable ways
in which, unless prevented, such properties
would cause harm to persons or property.
Most recently (1977-80)Dr. Yo~ngwas
the Manager of Tschn cai Publlcat ons far
the Chemical Manufacturers Association.
Dr. Young taught for many years ag King's
College in Pennsylvania and was a Visiting
Professor at Carleton University in Dtfawa.
He tauaht for seven vears in Sotaheastern
Jnwd States and war assoclald wlth the
lSlS protect at F orm State Unlvers ty
0 V o q lo the a h of several art.cles
on the teaching of chemistry, most ofthem
published in Uw JOCRNAL OF CHEMICAL ED
UCATION. These and other publications, in-
cluding more than a dozen books, have
sbesed IBbO(atmas a meansot insbuction
and the mponance 01 amtegoes des gned
toenhance ind vtom student contacts worn
their professor in b& large and small class
environments.
Recently or currently ha was or is in-
volved with nationally based groups. He
sewed for many years as Secretary of the
ACS Division of Chemical Education and
memoel 01 the Boam ol Publlcat on of tne
Jomal of Chem ca Eo~catlon,and a so IS
or has been a member of various ACS
Council comminees, chairman of various
committees and subcomminees, or a
member of such, in the ACS Divisions of
Chemical Health and Safetv and of Educa-
t m of NSTA, and other organ zations. I-
clJdmg tne Nat#onalAov saw Co~ncdon
CO ege Chemtslry He is a fe low of the
AAAS and a founding (charter)member of
me American Conferenceon Chemical La-
beling.
Volume 59
edited by
University 01 Idaho
MOSCOW, Idaho 83843
From this assembled information the label is
prepared, according to the following out-
line:
1) State the name of the chemical or if a
mixture, the names of the potentially haz-
ardous components.
2) State one of three degrees of potential
hazard, using one of three "signal" words,
Danger, Warning, or Caution (in order from
most to least hazardous-by definition).
3) Describe the potential hazards in short
statements. such as "Harmful if swallowed."
"Flnmmnhle." "Cause; revere burns." etc.,
ordering these wirh the most likely ur most
adverse cffwrs first tu the least likely or lea91
adverse last.
4) Describe the steps to be taken hy the
user in order to avoid the hazards that miaht
hrief hut nmplrte rtatemmlu,such as"Wa*h
thoroughly afwr handling," Keep away inm
heat, sparks and flame," "Wear protective
clothing including face and eye protection
and gloves," etc., again ordering these as
above.
5 ) Statements oertainine to first aid
treatmmt, spill clmn-up, fire fi~hting, stor-
age, err., fbllow, along uith any aprcinl ~ n -
structions that may pertain to the rhrmicsl
because of its unique but not well-known
properties. As an example of the latter, labels
for cyanides would describe the use of amyl
nitrite, a unique antidote for cyanide poi-
sonine.
iic,te particulnrly that the preceding five
steps oulltrze the procedure for the prrpnm-
t i m of labels. The nhwe d r s ~ r i p t i wis~hy no
means a complm dwuwVm uf the prurrd~ue
hy which asatisfnctory lnlwl is prepared.
With . o r r h a.~ s ofrrr e x r r v t i u n s , a l l e x ~ ~ ~ r i ~
ments performed by ~"dergraduates in
chemistry laboratories have features that can
make the performance of these experiments
hazardous. For almost all of these, however,
it is possible to take precautions in their ex-
ecution so as to prevent such features from
causing harm. If it is impossible to take the
appropriate precautions, the experiment
should not be ~erfarmed.In this paper I
(Continuedonpage A266)
Number 9 September 1982 A265

propose a procedure which if followed iden-
tifies an experiment as unreasonably haz-
ardous or indicates the precautions t o he
taken that render the experiment acceptable
for assignment to undergraduate students.
This procedure follows in parallel form the
procedure used to prepare labels, as will be
seen.
Procedure for Evaluating Experiments
Of all the experiments common to under-
graduate laboratory instruction, one stands
out as distinctly hazardous (fatalities have
resulted from its execution by students). A
detailed evaluation of this eiperiment will
illustrate the proposed procedure:
Stating the Experiment
The experiment (if indeed it is a true ex-
periment) is the generation of oxygen by
heating a mixture of potassium chlorate
and manganese dioxide, with potassium
chloride as the major solid residual
product.
Choosing Degree of Hazard
Following our parallel with labelling we
next choose the "signal" word, for which I
propose a "degree of hazard" statement in-
stead.
Very High Degree of Hnrard-if i t is for-
seeable that a careless student fumbling
A266 Journal of Chemical Education
the directions could cause a loss of life or
serious permanent injury.
High Degree of Hozard-if i t is forseeable
that a careless student fumbling the di-
rections could cause permanent but not
serious injury.
Moderate Degree of Hozord-if it is for-
seeable that a careless student fumbling
the directions could cause serious but re-
versible injury.
Low Degree of Harard-if it forseeable that
a careless student fumbling the directions
could only cause a minor and reversible
injury.
If more than one degree of hazard applies,
the most serious degree is selected for the
degree of hazard statement. Any experiment
classified as Very High or High Degree of
Hazard should not be assigned to students.
As performed in the past, the thermal de-
composition of KC1O8 has resulted in fatali-
ties. Therefore, Very High Degree of Hazard
applies. Unless the forseeable risk can be re-
duced, this experiment should not he per-
formed by students. The next steps in the
proposed evaluation procedure will show, for
this or any other experiment, either how the
risks can he reduced or that they cannot
he.
~escribin
Potential
~ Hazards
Tocutninue the parallel uith lahrling, the
reasonably fc,meeal>lrtmmrds are li>ted,di.
vided into these categories:
Those due to-
Apparatus
Separate chemicals
Experimental procedure
Inadvertent chemical spills
Routine clean-up and disposal of resi-
dues
Environmental effects
Violation of Occupational Safety and
Health Administration Reeulations
~ ~
Taking r h r v in order, thr Appnratu cnt-
rgury indudes cuttiuy n lenyth o t ' , h i tub-
ing, firr-polishing the rndi.nnd hending it in
the center to approximately SO9; inserting
this tuhe into the hole in a stopper; and using
a test tuhe that is not thoroughly cleaned af
all combustible residue or which mav contain.
say, a hit of fiber from a test tube brush.
The potassium ehlorate may he partially
decomposed, in the reagent bottle, into a
variety unstahle compound* rontnining
chhrine in unf2rniliar oxidationstatrs,surh
as -5 2.3 C.rrc.'l'hat is,chlor~rcssuhirctrd
. ..&eratures
to varvi'ne . in storaee are dtered
in U I I U S U ~ I way* and brrome urwtahlr to
further heating, sharp impart, fri rtlon. ' etc.
Porsible use of a black pmvdered i u t ~ m n c e
other than manganese dioxide is a well-
known student error, with dramatic conse-
quences if the mistaken black powder is
powdered charcoal, for example.
The toxicity of the separate chemicals
should he evaluated. See "RTECS" (2);it is
probably the most readily available and
complete toxicity reference, even if it is not
alwaya as reliable as one would wish. Ac-
cording t o this referenceand using the crite-
ria for "Toxic" and "Highly Toxic" from
reference (11. .
. . . ootassium ehlorate is neither
h~ghlytoxic nor tux^ nnd manganew d k d e
may, at molt, perhaps he imic ,the r i t d data
cnnn8,r be directl) applied to the criteria
given in reference (I)).
T o evaluate carcinogenicity, use (3) and
( 4 ) , or equivalent. Neither of the chemicals
are Listed in references (3) . . and (41:
. . . bv
" defi-
nition therefore, they are not carcinogenic,
nor suspected of being carcinogenic.
 Questions relat~dto teratogenirity, po.
tenrial genetrr damage, emhry<,frto-toxirlty,
ete., are by no means settled for any but a few
chemicals-none of which is likely to he used
in an undergraduate laboratory course, any-
way. At this time, perhaps it is prudent to
follow reasonable precautions to avoid in-
gestion, inhalation, and skin contact.
Reasonably forseeable hazards in the
procedure include the presence of a small
envnb of mbber from the stopper falling into
the potassium chlorate in the bottom of the
test tube; a cracked test tube because of too
rapid initial heating; or too rapid cooling if
water is sucked into the system when the heat
source is withdrawn from the test tuhe after
oxygen has been evolved, and consequent
flying glass shards and spilled, hot, potsssium
chlorate onto eomhustihle materials nearby
on bench or floor; and the toxicity of the
product, potassium chloride. Using the ref-
erence cited above, potassium chloride is
toxic, but not carcinogenic nor suspected to
be so.
This brings us to forseeable hazards in the
clean-up and disposal steps. I t is hazardous
to discard any undecomposed potassium
chlorate into a waste container that has, or
will possibly have, any combustible material
also tossed into it.
Hazards from environmental effects are
probably minimal and by definition are
eliminated if the requirements of the Re-
source Conservation and Recovery Act are
followed. Discussion of this matter is beyond
the scope of this paper. Apply to your local or
regional Environmental Protection Agency
Office for information about what is re-
quired.
Occupational Safety and Health Admin-
istration Regulations apply only t o employ-
ees, not to students. But prudence suggests
that, in a practical sense, students he eon-
sidered as though they were employees. The
most likely to be violated provisions of
29CFR1910 are those embodied in (5).
However, to be practical, equivalent or in
some cases more conservative human expa-
sure limits are found in (6).According ta both
(5)and (6)only manganese dioxide poses an
exposure hazard; the amo& of dust in the
air should not exceed 5 me oer mVcdculated
as Mn in the dust) forank:hr/day; 40 hdwk,
exposure.

Descrlbe Steps to Avoid Hazards

Next, we examine the above-described,
reasonably forseeable hazards to determine
if any, or all, can be eliminated or reduced in
magnitude. Taking them in order:
1) Make sure that all glass tube endsare fue
polished.
2) Caution students that glass that is hot
enough t o burn flesh looks exactly the
s a m e a s glass that is cool; have burn
ointment ready.
3) Caution students to protect their hands
when inserting, or removing, glass tubing
from stoppers and insure that every
student knows how t o carry out this
precaution.
4) Make sure that d l apparatus, hut the test
tubes in particular, are scrupulously
clean.
5) Be sure that only fresh-say not more
than 6 months old as received from the
supplier-potassium cblorate is available
(Continued on page A264

Volume 59 Number 9 September 1982 A267


to the students.
6) Make sure that the only substance that
even half-way looks like a black powder
that is available to the students is man-
ganese dioxide.
7) Insure that before s student inserts the
inspected for loose, partially loose, or
dangling particles of rubber stopper and
that all such particles are removed from
the stopper surfaces and from the glass
tubing before this assembly is fixed in
place in the test tube.
8) Enforce rigorously the requirement that
every student in the laboratory a t least
wash their hands and arms thoroughly
with soap and water before leaving the
lab a t the close of the period.
9) Be sure the students will heat the test
tube gently to start with.
10) Be sure that students will remove the
delivery tube from the water in the
pneumatic trough before they remove the
burner from the test tube.
11) Insure that there are no combustible
materials onto which hot potassium
chlorate might fall, or come in contact
with, in the event a test tube does
crack.
12) Rigidly enforce the rule for wearing ad-
equate eye protection.
13) Require the students to perform their
work usine a sturdv safetv shield for
A268 Journal of Chemical Education
inspected and in good condition, are
available and that students can use them
competently.
15) Have sufficient sodium thiosulfate
(perhaps 1 or 2 kg) available to cover any
spilled potassium chlorate. Be prepared
to add water to the spilled and covered
area, and to clean up the mess (and
promptly destroy any rags or cloth im-
pregnated with potassium chlorate so-
lution).
Note: Information concerning spill
clean-up procedures far a variety of dif-
ferent chemicals is available from sev-
. , but note that man" of
eral sources (7).
the recommended procedures violate
the spirit or the letter,or both,of the re-
cent Resource Conservation and Recov-
ery Act.
16) Provide a special waste container for
residues from the experimental work,
and enforce the rule for its exclusive use
as a place to deposit spent chemicals,
only. (Be sure that no foreign materials
get into this container and dispose of the
contents properly.)
17) Caution students, and employees, to not
deliberately inhale manganese dioxide
dust. (Other than this, no special provi-
sions to follow OSHA regulations seem
applicable to this experiment.)
If, after review, it is clear that d l forseeable
hazards have been identified, and if i t iscer-
tain that the appropriate precautions derived
therefrom can be fallowed, then i t would
seem reasonable to assign this experiment a
hazard class of Moderate Degree of Hazard,
and to include i t in the curriculum if it is
deemed pedagogically desirable t o do so.
To summarize. before assirnine anv ex-
s t u d e n t s , it is t h e reaponzihility of t h e pro-
fessor t e n e h r r i n s t r u r l u r in r h n q e t o d r ~ e r -
minr that t h e degree of hnzard of t h e exper.
iment is no greater than Moderate.
To carry out this responsibility it is nec-
essary to, first, identify every reasonably
forseeable hazard; second, t o ascertain
whether any of such hazards can be elimi-
nated or reduced in magnitude; third, t o
evaluate the degree of hazard when the pre-
cautions that can he taken to eliminate or
reduce hazards are carried out; and fourth, if
the then ascertained degree of hazard is
Moderate or less, to rigorously require stu-
dents to follow the precautions determined
to he necessary.
Literature Cited
11) Americsn National Standard for the Precautionary
Labeling of Hazardous Industrial Chemicaln. 2129.1.
~ m e r i e a n~ a t i o n a lstandards ~ n a i t u t s ,~ e ~wo r k ,
,.z,n.
"-"
12) Reeistry of Toxic Effects of Chemical Substances,
Government Printing Office. GPO Stock No. 017-
033-W86fi-I. We~hindnn.DC. 20402. 1979.
@I 45FR (the Federal R&&, vdume 45) pages 53672-
53679. Government Printine Office. Wahineton. DC.
(4) Carcinwn Aeaessrnent GmnpP~ListptfCarcinogena Ithe
T A G List"), Occupatiand Safetysnd Health Admin~
h e t i o n DocLelOfh Wa3hingl.m. DC, April 22,1980.
Note: This reference ia currently being revised: a "fi-
nalized publication probably will not b. available for
some time.
(51 Title 29, Codeof Federal Regulations, part 1910.IWo.
Government Printing Office, Washington, DC, 20402.
,980
(6) Threshold Limit Values for Chemiiil Ssbsttttts,etc,,
American Conferenceof Gov~rnmenfalIndustrial Hy.
gienists, Cincinnati, 1980. (Annually revised and up.
dated.!
~ ~
(7) Same k n . are: Aldrieh Chemicalcompany, annual
catalog. Milwaukee; Flynn Scientific, h a . , annual <st-
slog, Bstavia, IL;Guide for Safety in the Chemical
Lahrato~.2nded..VsnNustrandReinhald.NewY"rk.