The Chemical Adventures of Sherlock Holmes
The Case of the Stoichiometric Solution
Thomas G. Waddell and Thomas R. Rybolt
University of Tennessee at Chattanooga, Chattanooga, TN 37403
The following story describes a chemical mystery with
an emphasis on the utility of stoichiometry calculations.
This is the fifth article presenting a scientific problem in
mystery f o m in the context of the popular and beloved
characters Sherlock Holmes and Dr. Watson (14). There is
a break in the story where the reader (students and teach-
ers) can ponder and solve the mystery. Sherlock Holmes
provides his solution in the paragraphs following this
break.
The Story
"It's a puzzle to me, Mr. Holmes," said Inspector Tobias
Gregson. "Bishop was found a t the old limestone quarry in
a small rwm, locked from the outside. Dead as a flounder,
but without a bruise, a wound, or a mark on him."
"Curious, indeed" replied Mr. Sherlock Holmes. "But a
case of homicide, nevertheless."
'That's the way it looks to me." Inspector Gregson, the
tall and flaxen-haired Scotland yard officer, flapped his
ever-present notebook on his knee as he and Holmes
leaned toward each other across our brandy table at 221B
Baker Street. Holmes always regarded Gregson as the
smartest of a bad lot a t Scotland Yard and their wllabora-
tion was marked by a mutual respect often lacking in
Holmes' dealings with Gregson's arch rival at the Yard, In-
spector LeStrade.
"Bishop was one of the last employees of the old quarry,
Mr. Holmes. They were cutting back and it was either
Bishop or . . . . " he opened his notebook. . . . "one of his
coworkers Elmer Dunbar or John Mackenzie who was
going to be axed."
"Have you talked to Dunbar and Mackenzie?" Holmes in-
quired.
"Certainly," Gregson countered. "We were a t Dunbar's
flat this morning. He keeps snakes, of all things! "A shud-
der of disgust shook Gregson's narrow shoulders.
I felt compelled to inteject. "Shades of The Speckled
Band, Holmes! We may need our clubs again on this inves-
tigation."
Holmes ignored me. 'What have you learned about Mac-
kenzie?"
"In addition to his work a t the quarry, he runs a rather
peculiar business out of his flat," said Inspector Gregson.
"When we stopped to see him, we found several bottles
marked Acidum Aceticum Glaciale."
"Glacial Acetic Acid," said Holmes, leaning back in his
chair. "Rather nasty stuff and quite corrosive to human
flesh. However, it does find some use in the removal of
warts and moles."
"Quite right," said the surprised Inspector. *He had a
sign on his door giving notice to just such a business--wart
and mole removal.
"Great Scott," I said. "Do you suppose Mackenzie poured
glacial acetic acid upon the poor fellow?"
Holmes cast an annoyed glance in my direction. "My
dear Watson, need I remind you that Mr. Bishop had no
marks on his body. I usually find it most efficacious to for-
mulate a theory after all relevant facts are known and not
before."
Holmes turned back to the Inspector. "What else have
you done, Inspector? Bring me up to where you are."
"Bishop had one friend, Mr. Holmes, an acquaintance,
really, a Mr. Burke Lyons. He's a vinegar and food oil man-
ufacturer over on Wellington Street. It seems that Lyons
owed Bishop money; the two of them were involved with
quite a bit of gambling. I can't for the life of me figure what
killed Bishop in that locked room, Mr. Holmes, not to men-
tion who. I would be grateful if you and Dr. Watson a u l d
take a run out to the quarry with me to look things over. "
"We shall be most delighted, Inspector," Holmes cheer-
fully replied. 'Watson and I are a t a low ebb, are we not,
Watson? London's criminal element has momentarily sub-
merged to unimaginative scurryings of little interest."
It was a bright, summer day of dry and perfect weather
as the three of us climbed into Gregson's official cab for the
trip through the City to the limestone quarry where a Lon-
don criminal had apparently emerged in a fashion of inter-
est to Mr. Sherlock Holmes.
Arriving a t our destination we found that the small
guard hut was unattended and we passed into the yard of
the quarry without seeing a soul. Our cab glided smoothly
over the surface of dry, powdery limestone, and Gregson
took us immediately to where the body of Bishop had been
discovered. The sturdy oak door leading into the fatal room
stood before us.
"The key is still in the lock! " I exclaimed.
'We were told," Gregson replied, "that the key is left
there permanently. The caretaker and watchman, a Mr.
Clyde Montly, found the door locked as it should be, and
opened it to look in as a part of his routine. He discovered
the body this morning. The door cannot be locked from the
inside."
"What is this mom used for?" Holmes asked as he turned
the key and entered the small, darkened space.
Gregson followed him. "Storage of explosives, Mr.
Holmes. See. There are a few cartons left."
Holmes did not follow Gregson'~pointing finger. Instead,
Holmes was sauintina uv at the ceilinn.
-. at a small vatch of
sunlight visibie overhead.
"That's the ventilation shaft," said Gregson when he saw
where Holmes attention was directed. "Come with me. I'll
show you."
We left the mom and went into the bright sunlight. The
rwm in which the body had been found was completely
embedded in limestone walls and ceiling. On the ground
above the room, protruded a narrow stack, the ventilation
shaR from the room below. Holmes prowled the grounds
above the sunken room. While he did this, I wandered
about myself looking for clues to the strange death of the
man Bishop. Some 50 feet from the shaft I stopped short.
Below me in the powdered surface was the footprint of an
animal!
"Holmes, come here, quickly!" I shouted. With Holmes
and Gregson peering over my shoulder I asked, "Is it the
footprint of a Gigantic Hound?"
Volume 70 Number 12 December 1993 1003
 Gregson laughed. "Easy, Dr. Watson. The caretaker has
a large and foul mutt which keeps him company on his
rounds. We had best pay them a visit later on."
"What is this?" ~ o - ~remarked
e s in a serious tone. He
had left my side and had moved in a direction toward the
ventilation shaft. 'This is curious," he said. Holmes was on
his knees and Greeson and I followed his gaze to a sour-
smelling hole in tge limestone powder, about one foot in
diameter. The interior of the hole was rough and pock-
marked. T h i s hole was not dug by a shovel,"~olmesmur-
mured. Without moving from his position, his eves shifted
left to a pair of narrow,-but extremely deep wheel ruts left
by some heavily loaded wagon which had passed recently.
Holmes rose and with his characteristic long strides he
quickly walked away like some large bird toward a barn
where the vehicles used by the quarry were housed. He
was not gone long and upon returning was silent despite
our urgings to reveal his thoughts.
It turned out not to be necessarv to visit the caretaker. As
we conversed near the strange and malodoruus pot hole,
we suddenly heard a deer, roar and the beast that was the
cai-etaker'shog lunged up to us. The panting animal was
fat, short-haired, and of a color I cannot yet describe. The
limping caretaker himself followed behind his dog. "Down
now, Ginger, down, down," he addressed the dog affection-
ately
Gregson said, "Mr. Holmes, Dr. Watson, this is Clyde
Montly, the watchman and caretaker so-to-speak of .mis
~uw."
Mr. Montly bowed slightly to each of us and remained
silent.
After a few,moments, Holmes broke the silence with a
question. YMr.Montly, I only want to ask you one thing.
When you discovered the body after opening that room, did
you close the door again before you summoned the police?"
"No," Montly replied slowly, "I recall now that I left the
door wide open. It remained so I believe until the Inspector
here and his men arrived."
"I expected that to be the case," Holmes remarked to both
of us.
"Why was that, Mr. Holmes?" asked Gregson.
"Inspector, I need to make a few calculations, but I will
tell you this now. That deep wheel rut we observed near
the stack was not made by any of the wagons or vehicles
operated by the quarry."
Back in the cab, as we rattled our way through the
streets of London toward Baker Street, I heard Holmes
mutter to himself something about the room being seven
by seven by eight feet. Holmes scribbled furiously upon a
page tom out of the Inspector's notebook:
"Stoichiometry, Watson, stoichiometry," he mumblsd
when I inquired as to what he was doing. Soon he snatched
a second notebook page from Gregson, wrote out a sen-
tence or two, and handed the page back to the Inspector.
"You need to question this person more thoroughly, In-
spector. I have written on the note what incriminating ev-
idence I expect that you will find when you do."
Upon reaching our quarters and after Gregson had de-
partid hastily, we settled into our chairs. Holmes slowly
filled his briar pipe with tobacco from the Persian slipper
and began to explain it all.
Stop Here and Solve the Mystery
This mystery can be solved by remembering some Gen-
eral Chemistry Can you answer these questions?
(1) How was Bishop murdered?
(2) Who did it?
(3) What incriminating evidence did Holmes expect Gregson
to find?
1004 Journal of Chemical Education
The following paragraphs contain Holmes' chemical so-
lution to the mystery. Compare your solution to his.
The Solution
"Contrary to popular belief, Watson, a locked room mur-
der is usually quite simple in principle to solve. We, of
course, suspected that Bishop did not die naturally since
the room could only be locked from the outside. There is a
murderer then. but how was the murder done? What
caused 13ishop's death?"
"A snake, Holmes? As we encountered before?"
"h'o, Watson, a~suredlynot. There were no marks on the
body, no swelling. Rut just as we encountered in the Speck-
led Hand, my attention was drawn to a subtle mode of
entry into the locked mom."
"The ventilation shaft!" I exclaimed happily.
"Exactly, Watson. Recall that we examinedcertain pecu-
liarities about the limestone surface above the room and
near the stack."
"Holmes, I must apologize for my uneasiness over the an-
imal print. That paw print appears not to be related to this
case."
Holmes laughed memly "It is not, Watson! But what an
a ~ ~ r o ~ r ireminder
ate of the Gieantic Hound of bveone
dais! knd it served a good my good fellow. i&ay
not otherwise have noticed the sour-smellinghole and the
deep wheel ruts, which are very much related to the case."
"What do you mean, Holmes?"
"You have smelled that sourness many times before,
Watson. What is it? Where in this investigation did we en-
counter its name?'
I wondered. "Vinegar!" It suddenly came to me.
"Exactly, Watson, Addum Aceticum Dilutum. Vinegar is
a dilute solution of Acetic Acid, well done."
"But, what.. ."I stammered.
"So Lyons had access to dilute acetic acid and Mackenzie
had access to concentrated, 99 percent pure, glacial acetic
acid. As I mentioned before, I estimated the room to be
seven by seven by eight feet and the murder took place in
a limestone quarry. Surely the murderer is obvious. Lime-
stone is mostly calcium carbonate. The addition of two
parts of acetic acid to one part of calcium carbonate yields
one portion of carbon dioxide gas."
"It all fits, Watson. The pock-marked, sour-smellinghole
we found was formed when the murderer dropped some
acetic acid on the limestone. Remember from your school
days; we could write the equation as," said Holmes as he
scratched upon a piece of paper.
CaCO8 + 2CH8COOH+ Ca(CH3C00)2+ C02+ H20
"But, Holmes, where is the poison?"
"Watson, the murderer carried out this reaction in a
large, mobile vat and through pipes to the ventilation shaft
filled the room with carbon &oxide! Bishop died for lack of
oxygen!"
"And there would be no visible signs on the body." I knew
this from my medical training. "But Holmes, this reaction
could have been done by either Lyons with dilute acid or
Mackenzie with concentrated acetic add. How are we ever
to know which one did it?"
"Stoichiometry, my dear fellow. Surely you recall from
your school days the utility of the definite relations of
mass. volume. and amount between constituents in chem-
ical reactions."
"Well. I am not certain I recall all the details which I mav
have learned. I am afraid I still don't see how this
the key."
"I did that calculation in the cab. Look here. I paced
the room and measured its height by jumping up to the
ceiling. I can tell you the room was seven by seven by
eight feet. . . 392 cuhic feet. I happen to recall that one
cubic foot is equal to 0.0283 cuhic meters so the mom vol-
ume is 11.1cubic meters or 11,100 liters. As you may recall
or deduce there are 1000 liters in one cubic meter."
"Holmes, why do you convert our British units to those
used by the French?"
"Watson, the winds of change from the French Revolu-
tion have blown new ideas in many directions including
the system of metric units. With no disloyalty to my En-
glish roots, I must say that the metric system is far supe-
rior to our English system for scientific calculations. Now,
let us continue."
"I am afraid I still don't see in which direction to con-
tinue."
"What volume of vinegar, which is five percent acetic
acid, would be required to produce enough carbon dioxide
to fill such a room?" said Holmes. "Use equations, Watson.
Use stoichiometry!"
"One imperial gallon is equivalent to 4.55 liters and the
density of dilute acetic acid or vinegar is 1050 grams per
liter. Therefore, for a five percent solution we may write:
1.00 gal (0.0500) (4.55 Wgal) (1050 g acetic aeidn) =
239 g acetic acid
which means 239 grams of acetic acid per imperial gallon
of vinegar. Acomparison of the weight proportions of acetic
acid (60.0 glmol) and carbon dioxide (44.0 g Imol) in the
balanced chemical reaction where two acetic acids are re-
quired for each one carbon dioxide produced means that
120 grams of acetic acid are required for each 44 grams of
carbon dioxide."
"Therefore
(239 g acetic acidX44.0 g carbon dioxiddl20 g acetic acid)
= 87.6 g of carbon dioxide
I should mention to you that a term which has not yet come
to general use, but which I find most useful is the concept
of a mole, so that we may say (87.6 g carbon dioxide)
(moU44.0 g) = 1.99 moles of carbon dioxide."
"But, Holmes, I don't see how this tells us the volume of
vinegar necessary to produce the carbon dioxide to fill that
room of death."
"A combination of the laws of Boyle, Charles, and Avoga-
dro will provide the final clue. Consider the verfect gas law
where pressure times volume is proportional tomoles
times temperature. For a pressure of 1.00 atmosphere and
a temperature in the room of 77 Fahrenheit or 298 Kelvin,
we may write: pV = nRT or V = nRTlp and V = (1.99 moll
(0.08206 L atmlmol K (298 KY(1.00 atm) = 48.7 liters.
This tells us that each gallon of dilute acetic acid can gen-
erate 48.7 liters of carbon dioxide."
"To produce 11,100 liters of carbon dioxide would require
the use of 228 imperial gallons of vinegar. It can be done,
Watson. It was done. The deep wheel rut in the limestone
surface indicated a very heavy vehicle. . . . a wagon carry-
ing 228 gallons or more of vinegar!"
"But Holmes," I protested, "this proves nothing. Macken-
zie had access to concentrated acetic acid so instead of 228
gallons that Burke Lyons would have had to use, many
fewer gallons would be required to produce the same
amount of carbon dioxide. It would be much more conve-
nient to transport."
"That is correct, Watson. About one twentieth as much as
the five percent solution or only about eleven gallons. How-
ever, the deep ruts in the limestone clearly indicate a heav-
ily loaded wagon. It must have been Burke Lyons carrying
more than 2000 pounds of acetic acid. Deep ruts indeed."
"Could Mackenzie not have diluted his acid to a larger
volume." I said.
"Watson, I am most gratified that you would consider
this more subtle possibility. However, Mackenzie did not
know Lvons so there would be no reason to choose such a
more awkward means to transport his acetic acid. Also
consider the fact that Mr. Mackenzie lived in a tiny flat and
had no means to acquire barrels and vats and cany out
such a project without attracting considerable attention.
Whereas, Lyons was in the vinegar and food oil business
and routinelv used larce barrels and vats for the fermenta-
tion procesi to produGe his vinegar. Transporting large
quantities of vinegar would not be odd at all for such a
man. Once he had reached the isolated quarry, the addi-
tion of powdered limestone completed his necessary ingre-
dients. No, Watson, Lyons is the one."
"Holmes, do we know how Bishop was locked into the
room?"
"Gregson will sort that out, Watson. Most probably
Bishop and Lyons were meeting in the room to discuss
their money problems. A quick shove and a turn of the key
could well have locked Bishon in. And remember. that
quarry is not a populous placethese days. This alloould
easily have been done without the caretaker as a witness.
Remember also, that Clyde Montly left the door wide open
when he went to summon the volice. The room would have
been well freshened with oxygen by the time they arrived.
Inspector Gregson will find, I am sure, the wagon and vat,
as well as pipes used to reach the ventilation shaft, when
he questions Burke Lyons."
"Holmes, I am always impressed with how often chemi-
cal principles apply to solving practical problems. The
knowledge that I acquired during my college days has un-
fortunately left me. I must brush up so that I can be of
more able assistance to you in the future."
"Indeed, Watson. I thoroughly expect that these chemi-
cal adventures will continue as long as you and I can main-
tain the game afoot."
Literature Cited
1.Waddell,' G.: Rybolt, T. R. J. Chom.Educ 1989,66,981.
2. Waddell, T C.;Rybolt, T R. J. C h .Edue 1990.67, 1007.
3. Waddell, T G.;Rybolt, T R. J. Chm.Edw. 1B1,68,1023.
4.Waddell, T G.; Rybolt, T. R. J. Chom.Edue 1994,69,999.
Volume 70 Number 12 December 1993 1005