ISSN 10637788, Physics of Atomic Nuclei, 2010, Vol. 73, No. 14, pp. 2296–2300. © Pleiades Publishing, Ltd.

, 2010.
Original Russian Text © E.I. Grishanin, 2009, published in Voprosy Atomnoi Nauki i Tekhniki. Seriya: Fizika Yadernykh Reaktorov, 2009, No. 3, pp. 20–26.

The Role of Chemical Reactions in the Chernobyl Accident

E. I. Grishanin
Russian Research Center Kurchatov Institute, pl. Kurchatova 1, Moscow, 123182 Russia
email: egrishanin@orexovo.net
Received February 12, 2009

Abstract—It is shown that chemical reactions played an essential role in the Chernobyl accident at all of its
stages. It is important that the reactor before the explosion was at maximal xenon poisoning, and its reactivity,
apparently, was not destroyed by the explosion. The reactivity release due to decay of Xe235 on the second
day after the explosion led to a reactor power of 80–110 MW. Owing to this power, the chemical reactions of
reduction of uranium, plutonium, and other metals at a temperature of about 2000°C occurred in the core.
The yield of fission products thus sharply increased. Uranium and other metals flew down in the bottom water
communications and rooms. After reduction of the uranium and its separation from the graphite, the chain
reaction stopped, the temperature of the core decreased, and the activity yield stopped.
DOI: 10.1134/S1063778810140073

There is a vast technical literature devoted to the
first stage of the catastrophe at unit IV of the Cherno
byl Nuclear Power Plant (NPP), that is, an uncon
trolled increase in the reactor’s power [1]. There have
not been any publications on the study of the processes
which occurred after the explosion of the reactor.
Research into the condition of the accident at unit
IV by drilling holes has led to surprising results;
namely, the reactor lacks graphite stacking and fuel but
has concrete structures which have remained from the
destroyed room where the drum dividers were located.
Traces of the impact of high temperature are absent
and, in bottom rooms, there is no more than 10% of
the fuel in the form of lava fuelcontaining masses [2].
In [2], to explain the facts above, an interesting ver
sion has been proposed. According to it, after the
increase in reactor power to 10000%, evaporation of a
portion of the fuel and destruction of the zirconium
highpressure tubes took place. The authors state that
the part of the core in the southeastern sector “worked
as nonoptimal nuclear rocket engine,” which led to
the damage of the support structure there and precon
ditioned the presence of the socalled lava masses,
containing 10% of the uranium load of the reactor.
High vapor and gas pressure within the graphite
stacking destroyed the steel case of the reactor, which
was designed to allow for the breakage of only one
highpressure tube (it was able to hold an excess pres
sure of no more than 3.5 bar). Then, upon the impact
of pressure, the graphite stacking, together with the
remaining fuel, was ejected out of the underground
concrete silo. This is the explanation of the first explo
sion. When it flew out, the core instantaneously lost all
water, because of which a positive reactivity on the
order of 4.5 fractions of delayed neutrons appeared.
Runaway on prompt neutrons up to a power of
47000% led to evaporation of all fuel and graphite in
the core. After that, nothing essential took place in the
silo of the reactor as nothing else could burn up. Then,
three concrete blocks of the destroyed box of the drum
divider fell down into the empty silo, followed by the
Elena upper metal structure falling down on its edge.
However, this theory fails to explain many well
known and documented facts, namely, a relative “lull”
for 20 h after the explosion when the worst seemed to
be in the past; a sharp increase in the yield of radioac
tivity after 20 h; active burning of graphite; a fourfold
rise of radioactivity from May 1 to 6; a decrease in
radioactivity release by 1 million times after May 6.
It can be easily shown that the graphite could not
evaporate. First, it produces only 6% of the power of
the core. Second, its weight is 10 times greater than
that of the fuel, while its thermal capacity is three
times greater than the heat capacity of the fuel. There
fore, upon runaway of the reactor, the graphite is
hardly heated.
For instance, if the fuel is heated by 1000°C
because of reactor runaway, the graphite will only be
heated by 2°C; if the fuel is heated by 3000°C and
evaporates, it will fly out of the technological channel
as if the latter were the barrel of a gun, and the graphite
temperature rise only by 6°C. This property of the
highpower channeltype reactor (RBMK) is well
known to nuclear plant operators. A portion of the
graphite could fly out of the reactor owing to mechan
ical coalescence with the zirconium tube of the tech
nological channel.
The goal of this study is to clarify the events that
took place during the failure with chemical and
nuclear reactions taken into account. It is widely
accepted that an uncontrolled chain fission reaction

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 THE ROLE OF CHEMICAL REACTIONS IN THE CHERNOBYL ACCIDENT
occurred in unit IV of the Chernobyl nuclear power
plant, which was preconditioned by flaws in the reac
tor’s structure and breach of the procedures by the
operators [1]. What caused the catastrophe is the same
as the reasons for the failure at unit I of the Leningrad
NPP in 1975 [3, 4].
All RBMKtype reactors have the following inher
ent feature: there is a spatial instability of the neutron
field owing to the large size of the reactor compared to
the migration length and the presence of a positive
feedback with respect to the power (via the steam coef
ficient of reactivity). Many critical masses exist in the
core of a large reactor and the connection among them
is weak; the RBMK is large both in diameter and in
height. The effect of the neutron field’s instability was
not taken into account when unit I of the Leningrad
NPP was designed. These spatial fluctuations of the
neutron flux had to be neutralized by means of moving
control rods manually by the operator.
It is no surprise that the moment came when the
operator could not handle the control rods. As a result,
in December 1975, more than 42 fuel assemblies over
heated. The temperature of the claddings of fuel ele
ments contained in the fuel assemblies hit 1600°C.
Only two highpressure casings were destroyed, how
ever; otherwise, the effects of this accident could have
been like those at unit IV of the Chernobyl NPP. The
failure at the Leningrad NPP and the Chernobyl
nuclear accident have the same nature and differ only
in the scale of the consequences, which, in turn, were
due to different initial conditions (mainly, xenon poi
soning).
Under the decision of a government commission
which examined the causes of this accident, a set of
technical solutions increasing the stability of the spa
tial power distribution was developed. This set
included a system of local power governors (LAR).
Every relatively large spot in the core had its own auto
matic power governor. The system supported at a sat
isfactory level the required power distribution, i.e., the
ratio of powers between nearly independent areas of
the core. It is for this reason that the large reactor had
the procedural limitation on the minimum number of
control rods, which was violated by the operators dur
ing tests.
On April 16, 1986, unit IV of the Chernobyl NPP
was subjected to scheduled tests of a standard security
system before it was put into operation. Analogous
tests were conducted at other RBMK units. This sys
tem was not timely tested and it was commissioned at
the startup of unit IV in Chernobyl. It relies on the
rundown of the turbine generator for electricity supply
to the main circulation pumps (MCPs) upon their de
energizing.
The system was developed for reactors of the
VVER440 type, which have sealed pumps with a very
low rundown value; this was the reason for the danger
ous overheating of fuel elements upon complete zero
ing of the MCPs. It is doubtful whether such a system
PHYSICS OF ATOMIC NUCLEI Vol. 73 No. 14 2010
2297
should be applied at RBMKs, since an RBMK is able
to work on natural convection at a power of up to 40%.
The fact that the regulating bodies permitted the oper
ation of the unit without this system speaks for the
extent of its futility.
During testing, it was planned to bring the reactor
to the power of 200 MW, which is approximately
equivalent to the power of the residual heat increase,
then deenergize half of the MCPs, and test their elec
tricity supply by means of the turbine generator’s run
down.
Prior to the tests, the reactor was strongly poisoned
with xenon, which, according to our estimates, tempo
rarily decreased the reactivity margin by 2.9% and sig
nificantly increased the steam effect of reactivity. This
is of fundamental importance. Such a test conducted
under the same conditions will result in a similar
catastrophe. In the process of chemical reactions, an
additional release of positive reactivity took place.
Before the explosion, the temperature of the
graphite stacking was approximately 500°C. The con
sumption of coolant exceeded the nominal value
owing to the switchingon of the reserve MCP. For the
large loss of reactivity under conditions of the xenon
poisoning, in order to bring the reactor to the required
power, the operators had to withdraw from the core a
substantially larger number of control rods than the
procedure allowed. As a result, some sites in the core
were not regulated by an LAR. Therefore, from the
viewpoint of the neutron flux instability, the situation
at unit IV was close to the conditions at unit I of the
Leningrad NPP in 1975. Seemingly, it was the south
eastern sector where the majority of control rods were
removed. Hence, the initial stage of the development
of the accident at unit IV was virtually the same as at
the Leningrad NPP in 1975.
Some channels overheated owing to the uncon
trolled increase in the neutron flux in the absence of
local governors. Compared with the accident at the
Leningrad NPP, the situation was further aggravated
by the fact that the reactor was subject to xenon poi
soning, where the steam effect of reactivity became
significantly higher, as well as that the button for drop
ping all control rods was pushed (in this case, it pro
duced a positive reactivity at the start of the motion).
As a result, the number of overheated channels was
several times higher than in the accident in 1975. The
power increase was accompanied by boiling of the
coolant.
When the crisis of heat exchange arose and the
temperature of the zirconium claddings of fuel ele
ments in part of the core reached 1000°C, hydrogen
started to form through the steam–zirconium reaction
Zr + H2O = ZrO2 + H2, producing 1000 normal cubic
meters. This led to an acute increase in hydraulic resis
tance in the circulation loop of the coolant and to a
boost in the reactivity for the reason of displacement
of water out of the core. As a result, in the fourth sec
ond after the actuation of the emergency protection
2298 GRISHANIN
rods (AZ5), MCPs with working electric drives
decreased the consumption twofold in accordance
with their force–consumption parameter, which is a
reliably documented fact. At the same time, MCPs
working in rundown stopped immediately, which is
also documented by way of unreliable readings of their
sensors of consumption (backflow of water through
MCPs). Two seconds later, all MCPs resumed their
consumption, which should be unambiguously inter
preted as multiple destruction of zirconium tubes of
the technological channels, bearing the pressure of the
coolant, since in this case, the hydraulic resistance in
MCPs sharply fell.
The manifold destruction of highpressure tubes is
preconditioned by that fact that, with the further
increase in the reactor’s power, the temperature of the
superheated steam exceeded 1000°C and the tubes
made of the zirconium alloy lost their firmness. This
happened in the southeastern sector of the reactor. At
the multiple nearly simultaneous rupture of the high
pressure channels, a powerful hydraulic shock took
place to deform the reactor’s support and drop it 4 m
lower. Such a shock could have caused corresponding
seismic disturbances and underlies the hypotheses
about the seismic reasons for the Chernobyl catastro
phe.
After the destruction of many highpressure chan
nels, steam and hydrogen with a temperature of
1000°C begun to penetrate the graphite stacking,
where the endothermic chemical reaction H2O + C =
CO + H2 occurred. The role of other chemical reac
tions was insignificant. At the same time, the reactor
worked as giant gas generator with a nuclear source of
heat. When the excess pressure in the graphite stacking
reached 3.5 kg/cm2, the vessel of the reactor was
destroyed. This was the first steam explosion which
overturned the upper structure of the reactor and
ejected part of the fuel and graphite.
Hydrogen and carbon monoxide (CO) came from
the reactor into the Central Hall in an amount of over
10000 m3; they mixed with the air to produce an
explosive mixture. The explosion of the mixture was
initiated by pieces of graphite which had a temperature
on the order of 500°C. This was the second massive
explosion which provided the appropriate nature of
the destruction of the reactor building and caused the
presence of soot at the moment of the CO explosion
and the dark red color of the fire. Thus, the following
chemical reactions played an important part in the
explosion of the reactor of unit IV: the steam–zirco
nium reaction in the fuel channels and the formation
of CO in the graphite stacking.
Only part of the core exploded, in which control
was lost because of the removal of the control rods in
violation of the procedure. The remainder was in a
subcritical condition.
Further events during the accident can be conven
tionally divided into the following stages: (1) the first
24 h after the explosion; (2) the reactor’s attainment of
PHYSICS OF ATOMIC NUCLEI
power and the heating of the core before April 30;
(3) destruction of the claddings of fuel elements, con
figuration anew of the core accompanied by a further
increase in reactivity and temperature of the core, and
an increase in the release of fission products starting
on April 30; and (4) destruction of the zirconium high
pressure tubes and direct contact of the graphite with
fuel pellets from May 4 through 6.
During the first hours after the explosion of the
reactor, it seemed that the worst things had already
happened and the reactor would cool since the resid
ual heat output was falling rapidly. From the air, the
glowing core was seen at night and steam coming out
of the destroyed reactor was visible in the daytime.
At the same time, there was the following reaction in
the graphite stacking: 2C + O2 = 2CO. Other reactions
with the formation of CO2 were insignificant because
of the excess of graphite or lack of oxygen. At the time,
the initial temperature of the graphite was on the order
of 500°C, at which the rate of the reaction was low.
A small amount of CO mixed with the cold air in the
space over the reactor and had a relatively low temper
ature. Therefore, there was no fire over the reactor
during the first day.
The second stage began on the second day after the
explosion. The reactor started to attain power as a
result of the decay of iodine and xenon135 (termina
tion of xenon poisoning). The reactivity excess was
compensated by the corresponding increase in the
temperature. The release of radioactivity rose sharply.
Because of the heatup of the reactor, the rate of the
chemical reaction 2C + O2 = 2CO increased sharply
and a fire burst out over the reactor, in which the car
bon monoxide was burning. Approximately on
April 29 after practically complete decay of iodine and
xenon, the maximum reactivity Δk = 2.9% was
released, and the reactor reached the maximum tem
perature, which can be assessed as follows.
If we assume that the Doppler coefficient is equal
approximately to dk/dt = 2.9 × 10–5 K–1, then the tem
perature of the fuel averaged over the volume of the
core should increase by the value of ΔT = Δk/(dk/dt) =
0.029/(2.9 × 10–5) = 1000°C. Owing to extensive nat
ural air circulation, the bottom of the reactor had a rel
atively low temperature on the order of 30°C. Hence,
the maximum temperature of the fuel must have been
2000°C in order to produce the average fuel tempera
ture of 1000°C. The release of positive reactivity after
the termination of xenon poisoning determined the
condition of the failed reactor, which was called later
the “active phase.”
The level of power established after the heatup of
the reactor was determined by the excess reactivity of
2.9% and the consumption of air via the destroyed
communications of the reactor by means of natural
convection. Air circulation in the ruptured reactor
explains many of the processes that occurred. It took
place at every site where heat was extracted. It is
important to note three parallel profiles of air circula
Vol. 73 No. 14 2010
 THE ROLE OF CHEMICAL REACTIONS IN THE CHERNOBYL ACCIDENT
tion. The first of them includes sections of channels in
the southeastern sector, whose bottom was destroyed,
and distributing headers and other channels destroyed
in the ceiling. The cold air arrived via the destroyed
channels of the southeastern sector to distributing
headers and channels ruptured in the ceiling. The air
cooled the fuel. Air consumption in this profile is esti
mated at G = 40 kg/s, and its thermal capacity is C =
1.0 kJ/(kg K).
With such air consumption, the power of the reac
tor is calculated as N = GCΔT = 40 × 1.0 × 2000 =
80000 kW. At the average temperature of the fuel, its
maximum value must equal 2000°C. The difference in
temperature between the fuel and the air coolant is
small owing to low power. Therefore, the heatup of
the air in the channels with the fuel amounts to
approximately 2000°C. Heat exchange in the active
zone due to endothermic reactions of metal reduction
is estimated at 3 MW. The increase or decrease in heat
exchange via chemical reactions will lead to the
increase or decrease in power, respectively.
The second loop of natural air circulation is formed
by the gap between the casing of the reactor and the
graphite stacking and the gaps in the graphite stacking.
Cold air arrives via the gap between the casing and
graphite stacking, then in the gaps in the graphite
stacking, and cools the latter and leaves via the upper
part of the destroyed reactor to the space above. The
third loop of air circulation in the premises beneath
the reactor cools the tubes feeding water to the reac
tor’s channels in the normal mode. There, the air
starts to circulate extensively when melted uranium
begins to reach these tubes.
Air, entering the channels with the fuel, actively
oxidizes, at high temperature, the zirconium claddings
according to the following chemical reaction: Zr + O2 =
ZrO2. As a result, the claddings of fuel elements were
destroyed.
The third stage of the process of the accident com
menced after the complete destruction and shedding
of the fuel element claddings in the channels. Accord
ing to calculations, removal of the zirconium clad
dings of fuel elements from the core leads to approxi
mately a 1.2% increase in reactivity. The average tem
perature of the fuel increases by approximately 350°C
and the reactor’s power increases to 110 MW. As a
result, the air temperature in the outlet of the reactor
and the fuel temperature in the core ceiling increased
to 2700°C.
At temperatures so high, the zirconium tubes of the
reactor channels started to oxidize and be destroyed
rapidly. In the upper part, they could even have
melted. This was the beginning of the fourth stage of
the accident process. Complete oxidation, shedding,
and melting of these tubes could have led to the
removal of a large amount of zirconium from the core
and the appearance because of that of additional reac
tivity on the order of 1.5%. Therefore, the power of the
reactor and its temperature could have risen to an even
PHYSICS OF ATOMIC NUCLEI Vol. 73 No. 14 2010
2299
greater extent. A chaotic strewing of the fuel pellets
and, probably, of a certain amount of fragments of the
oxidized zirconium channels took place in the upper
part of the active zone.
Such a change, which occurred from about April 30
to May 1, led to immediate contact of UO2 pellets with
graphite, and intense reduction of uranium oxide and
other oxides of fission products began, resulting in a
fourfold increase in emission of radioactivity.
In essence, the reactor worked as if it were a nonopti
mal blast furnace for the smelting of metal uranium,
plutonium, and fission products from their oxides. As
the reduced metal uranium continued to flow down,
the hightemperature zone dropped down. The pro
cess of reduction was like the burning of a candle.
Upon immediate contact, the reduction reactions
took the form C + UO2 = U + 2 CO2 and MeO + C =
Me + CO2. We made calculations of the change in iso
barisothermal potential (Gibbs’ energy) at atmo
spheric pressure and various temperatures in order to
assess the fundamental feasibility of the chemical pro
cess of uranium reduction by graphite. There, we used
the methodology and initial data on change in
enthalpy and entropy of chemical reactions taken
from [5, 6]. These estimates showed that the reaction
of uranium reduction with graphite was possible at a
temperature above 500°C in the absence of oxygen.
The absence of oxygen was ensured by intense oxida
tion of graphite at high temperature.
Reduced uranium (melting point of 1100°C) flew
down to the bottom steel tubes, through which the
coolant was fed and which remained in good condition
since they were cooled by air. The metal uranium
hardened in these tubes, and at the same time, ura
nium gradually left the graphite stacking. When the
process of reduction was over, the fission chain reac
tion ended since the uranium was isolated from the
graphite. The graphite burned out, and the release of
radioactivity decreased first by a 1000 times and then
by a million times, which occurred on May 6. The
metal plutonium sublimated at high temperature;
therefore, its concentration was low in the uranium.
In the southeastern sector of the reactor, the first
explosion damaged the support of the reactor and
coolantfeeding communications. Therefore, the
reduced uranium flew down to the bottom premises as
well, where it reacted with the concrete at a tempera
ture of 1100°C, forming socalled fuelcontaining lava
masses. Their amount tallied well with the estimate of
the superheated portion of the core obtained in [1].
The estimate of the time of the process after the explo
sion nearly coincides with the real duration of the pro
cess. One should look for missing uranium in the hard
ware of the water feed of the reactor, which was not
drilled. If metal uranium is discovered in the hardware,
this fact will confirm our theory.
Precisely because of chemical reactions owing to
the heat produced by the fission chain reaction, most
of the volatile fission products, i.e., gases, iodine,
2300 GRISHANIN
cesium, strontium, and plutonium, flew out of the
reactor and spread over the world. Only fission prod
ucts with a high boiling point remained in the
destroyed reactor. That is why the release of radioac
tivity decreased by a million times after May 6. High
heat fission products primarily remained under the
sarcophagus.
There ought to be a natural explanation of why
there are practically no traces of the hightemperature
impact in the reactor and how concrete blocks with
traces of paint ended up there. The concrete silo has a
gap over 0.5 m wide between the concrete and the
graphite stacking. After the explosion, cold air arrived
via the gap to further penetrate the graphite via cracks
and channels in the graphite stacking; in the graphite
layer, the chemical reactions mentioned above
occurred. The mixture of nitrogen and CO formed as
a result of these reactions at a temperature of approxi
mately 450°C came out into the space above the reac
tor, where it mixed with air and formed a fire torch,
which was visible to everyone.
CONCLUSIONS
A new version of initial events which led to the
explosion of the reactor of unit IV at the Chernobyl
NPP is proposed based on the instability of the neu
tron flux in the largesized reactor. The character of
destruction of the reactor hall speaks for the presence
of a voluminous explosion of the mixture of air, hydro
gen, and carbon monoxide.
The decay of xenon and iodine resulted in resump
tion of the fission chain reaction, the heat of which was
spent to reduce uranium oxide and oxides of pluto
nium and fission products. The attainment of the
power of about 80 MW by the failed reactor, with a fur
ther increase to 110 MW, caused the extremely grave
radiation effects a full day after the explosion.
Chemical reactions played a crucial part in the pro
cess of the catastrophe at unit IV of the Chernobyl
NPP at the stage prior to the explosion, during the
explosion, and after it; taking them into consideration
can explain important details. At the final stage, the
reactor worked as a nonoptimal blast furnace, where
oxides of uranium, plutonium, and fission products
were reduced to metals.
PHYSICS OF ATOMIC NUCLEI
Metal uranium is present in the bottom hardware of
the water supply to the reactor, and metal plutonium
sublimated, contaminating the 30km zone around
Chernobyl.
In the process of development of the accident, the
overwhelming majority of fission products with a boil
ing point lower than 2000°C left the reactor. Only
highheat fission products remained in the sarcopha
gus. Therefore, the contents of the sarcophagus do not
present any hazard from the viewpoint of a significant
release of radioactivity.
The author hopes that the publication of this paper
will inspire the interest of experts in a more careful
study of the role of chemical reactions in the Cherno
byl accident.
ACKNOWLEDGMENTS
The author is grateful to E.V. Burlakov for valuable
comments. Special gratitude goes to Candidate of
Chemical Sciences V.K. Popov for calculations justify
ing the possibility of the chemical reactions men
tioned in this paper.
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