RECOGNIZING LABORATORY

HAZARDS: PHYSICAL HAZARDS

DR. MUHAMMAD IMRAN RASHID

INCOMPATIBLES—A CLASH OF VIOLENT
PROPORTIONS
Incompatibles——A Chemical
Overview
Incompatible chemicals are combinations of substances, usually in
concentrated form, that react with each other to produce very
exothermic reactions that can be violent and explosive and/or can
release toxic substances, usually as gases
There have been many incidents involving incompatible chemicals
In these unintentional situations the risks are considerable since no
one is expecting the reaction to occur
There may be property damage due to fires or explosions if gases are
involved and these explosions can result due to rupture of containers
Cont…

It is worth noting that sometimes in the laboratory we mix dilute

solutions of incompatibles for some purpose, but because they are
not concentrated they do not react violently and only release limited
heat in their reaction
There are hundreds and thousands of chemicals and all possible
incompatibles mixtures can be memorized but combination of
different chemical groups can be learned
Most chemical reactions that are exothermic will be either acid–
base reactions or oxidation– reduction reactions
Cont…

Thus, as you think about any single chemical as something that may
have “incompatible partners,” you can ask:
Is this chemical a strong acid?
Is this chemical a strong base?
Is this chemical easily oxidized?
Is this chemical easily reduced?
Table 5.2.3.1 given in next slide presents a useful overview of the
most common incompatible classes of chemicals with examples
Incompatibles Chemicals——A Limited Listing
Acid–Base Incompatibles——Overview
most common incompatibles are acids and bases
Mixing acids and bases can produce violent, even explosive,
reactions that release a lot of heat (exothermic reactions)
a reaction between a strong acid and a strong base will be very
exothermic
strong acids reacting with weak bases and strong bases reacting
with weak acids can be dangerous, too.
Six strong acids and six strong bases are listed in tables in next slide
Cont…
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The exothermicity of the acid-base reaction will depend on the concentration of the
solution, Weaker concentrations are less dangerous
As an illustration of the danger of mixing strong acids and bases, let’s calculate the
heat released, and temperature increase, when mixing 100 mL of 12 M HCl and 100
mL of 12 M NaOH
The heat of reaction is −55.8 kJ/mol, which leads to 67 kJ of energy being released
from 1.2 mol of reactants
If the reactants start at room temperature, about 25 ◦C, the final temperature of about
109 ◦C suggests a very violent, uncontrolled reaction
Glass bottle might shatter from the rapid temperature change
mixture might cause dangerous spattering of a hot solution of a strong acid or base
Strong Oxidants and Reductants——An
Overview of Redox Incompatibles
Identifying chemicals that are easily reduced (strong oxidants) or
easily oxidized (strong reductants) is less simple, but there are some
guides
We can look at reduction potentials for various chemicals
Table 5.2.3.4 might help you identify strong oxidizing agents and
strong reducing agents
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Chemicals that are reactants at the top left of the table (boldfaced)
are very easily reduced and are therefore good oxidizing agents
Some trends to note are the elemental halogens and compounds
that have atoms in relatively high oxidation states, such as N(+5) in
nitrate and Mn(+7) in permanganate
Note that when oxygen is in an oxidation state that is greater than
−2, it is in an “oxidized” state
So, oxygen in peroxide is at −1 and oxygen in O2 is at zero
Cont…
Nitric acid and nitrate have been involved in the majority of incidents
involving incompatible chemicals
The virtue of good oxidizing power is simultaneously its greatest hazard
Another strong acid that is a very strong oxidizing agent is perchloric acid,
HClO4
It is quite likely that you have never used perchloric acid since it presents
unusual hazards
hot solutions are powerful oxidizers and pure perchloric acid explodes upon
contact with organic compounds and materials (such a cloth, wood, and
rubber)
Cont…

Permanganate is also a strong oxidizing agent and used in dilute form in

titrations but dilute solution are less hazardous
Hydrogen peroxide is an excellent oxidizing agent and at concentrations
greater than 30% present considerable fire and explosion hazards
Chemicals that are products at the bottom of the table (boldfaced) are
very easily oxidized (to the reactants shown in the half-reaction) and will be
good reducing agents
Many metals, called the active metals, oxidize easily and, as you might
guess, hydrogen in the −1 oxidation state (hydride) is also easily oxidized,
The substances are strong reducing agents
Cont…

A few more comments are helpful in using Table 5.2.3.4

Cont…

Sometimes chemicals react with each other

A classic example of this is nitric acid and acetic acid
This is not an acid–base reaction but instead is a redox reaction
acetic acid and nitric acid produce toxic NO2 gas:
CH3CO2H(aq) + 8HNO3(aq) → 2CO2(g) + 8NO2(g) + 6H2O(l )
This reaction has an obvious lesson for chemical storage: don’t assume that
the most common use of a chemical (e.g., nitric acid as an acid) limits its ability
to function otherwise
Storing these two acids together, poses hazard
Chemicals That React With Water——
Water-Reactives
We ordinarily consider water to be fairly nonreactive
Water-reactives are chemicals that react violently with water,
releasing large amounts of heat and sometimes flammable gases or
toxic gases, often resulting in fires or explosions
Cont…

As Table 5.2.3.5 shows, most notorious in this group are the alkali
metals—lithium, sodium, and potassium
In Table 5.2.3.3 you can see that these are the metals where the
cation has a large, negative reduction potential
Thus, any chemical that is the product of a reduction with a large,
negative reduction potential might be water reactive
There have been laboratory fires caused by the reaction of water
with these metals, particularly sodium and potassium
Cont…

Sodium is often used to “dry” organic solvents and fires have occurred
because researchers assumed that all of the sodium metal has been
consumed or reacted and have dumped the residue into a sink, where
water came in contact with unreacted sodium metal which caught fire
The equation below shows the reaction between sodium and water
that results in sodium hydroxide and the release of hydrogen:
2Na(s) + 2H2O(l ) → 2NaOH(aq) + H2(g)
When chemists or firefighters refer to a “metal fire” it is actually the
hydrogen gas that is produced that is on fire
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All of the reactions in the table 5.2.3.4 are acid–base reactions (unlike the
active metals above, which are redox reactions
When handling a water-reactive compound you should carefully plan how
you will use it in a manner that prevents contact with water, including
moisture in the air
In some cases, sloppy handling of the chemical, perhaps even in humid air,
will cause it to react slowly and prevent further use of the chemical as a
reagent
Finally, we note that many strong acids and bases with high concentrations
react violently when diluted with water due to large energies of solvation
Pyrophorics—Incompatibles with Air
Pyrophoric comes from the Greek word purophoros meaning “fire-
bearing.”
Pyrophorics are chemicals that ignite spontaneously in the presence
of air
Finely divided metal powders can be pyrophoric, as well as reactive
metal alloys, metal hydrides, and some metal salts
Calcium, zirconium, uranium, and magnesium powders are examples
of pyrophoric metals
Zn(s, dust) + 2H2O(l ) →Zn(OH)2(s) + H2(g)
Cont…

Lithium aluminum hydride, sodium borohydride, and sodium hydride are pyrophoric
hydrides that react with moisture in the air
The equation representing the reaction of a hydride with moisture in air is shown below:
LiAlH4(s) + 4H2O(l ) → LiOH(aq) + Al(OH)3(s) + 4H2(g)
While hydrocarbons are thermodynamically unstable in an oxygen-containing
atmosphere, they are kinetically very slow to react
However, many boranes (BxHy ) and silanes (SixHy ) are both thermodynamically
unstable and they react quickly in air
B2H6(g) + 3O2(g)→ B2O3(s) + 3H2O(l )
SiH4(g) + 2O2(g) →SiO2(s) + 2H2O(l )
Cont…

White phosphorus is P4, It spontaneously ignites in air above 35 ◦C

red phosphorus, black phosphorus are air-stable
Since white phosphorus is pyrophoric, it is stored under water to
prevent contact with air (oxygen)
The reaction of white phosphorus with oxygen in the air is shown in
the equation below
P4O10, is very water-reactive
P4(s) + 5O2(g)→ P4O10(s)
Cont…

When handling a pyrophoric chemical, and before you take the first
steps to open the container, plan how you will use it in a manner that
prevents contact with air
Pyrophorics should only be handled by chemists with the
knowledge and skills to work with these chemicals safely
Storing Incompatible Chemicals

Donot store incompatibles together especially where earthquakes

are possible
Natural weather event that could result in shelves collapsing and
broken bottles of chemicals mixing
If you keep your incompatibles separated, then the risk of
incompatibles coming in contact is reduced
As with all hazardous chemicals, you can reduce the risk by
minimizing the quantities of chemicals being used and stored
RAMP
• Recognize chemicals that you are using (or storing) that are considered to be “incompatible” with
other chemicals. If uncertain, do the necessary library or online research to learn more about
unfamiliar chemicals.
• Assess the risk level when using or storing these chemicals. Review chemical procedures to assess
the possibility that incompatibles might unintentionally mix.
• Minimize risks by using incompatible chemicals only when necessary and limiting quantities that
are used. Design experimental procedures to minimize the chance for unintentional interaction
between incompatibles. Store incompatibles in separate locations. Minimize storage volumes by
ordering only as much as reasonably necessary.
• Prepare for emergencies by knowing how to respond to unexpected reactions between incompatibles
and how to respond to spills.
Thank You