66

ICOM COMMITTEE FOR CONSERVATION, 2002 VOL I

Introduction
A rule of thumb stating that a 5C drop in temperature will double the chemical
lifetime of unstable materials has emerged for museums, analogous to the
laboratory rule of thumb that chemical reaction rates fall to one half for each 10C
drop. Erhardt (1989) demonstrated this museum rule by inspecting tables of values
calculated from the Arrhenius equation. It will be derived explicitly in this paper.
The interaction with relative humidity (RH) has been less clear, but both Michalski
(1993) in reviews of paper literature, and Erhardt and Mecklenburg in experimen-
tal work (1995) find that a power law fits the data best. In a recently published
guideline for archives, the author (Michalski 2000) reviews further data and
provides graphs for practical application. This article briefly summarizes that
material. Furthermore, it provides a theoretical derivation of the temperature rule
from fundamental constants, thereby suggesting that the rule is universal for all
chemically unstable materials held in museums.
From Arrhenius to a simple rule based on temperature change
The Arrhenius equation is widely used in conservation science studies of acceler-
ated ageing, as well as chemical engineering estimates. It is derived from a notion
of an energy barrier or activated state through which chemical reactants must pass:
(Dickerson et al. 1970: 786790)
1 (Note that the computer code convention of ^ is used to indicate the exponent,
rather than the traditional superscript.)
(1) k=Ae^(-E
a
/RT)
k: reaction rate constant, s
-1
A: frequency constant, s
-1
E
a
: activation energy, Jmol
-1
R: gas constant, 8.314 J mol
-1
K
-1
T: temperature, K
Since material lifetime depends on the reciprocal of the reaction rate k, an equation
for a lifetime, L
2
, at some other temperature, T
2
, compared to the lifetime, L
1
, at
a reference temperature, T
1
, can be derived from equation:
(2) L
2
/L
1
=e^([1/T
2
1/T
1
]E
a
/R)
L: lifetime, unspecified units
A rule of thumb based on double the life for a given temperature drop is an
exponential equation using base 2 rather than base e:
(3) L
2
/L
1
= 2^([T
1
T
2
]/T
d
)
T
d
: temperature drop that will double the lifetime
Abstract
Data on accelerated ageing and the
effect of temperature and relative
humidity (RH) are reviewed for
paper, film and magnetic media
studies. The activation energy for
most paper and film studies falls in
the range (80 to 120) kJmol
-1
. For
decay in magnetic media binder and
yellowing of damar resin, the activa-
tion energies fall in a lower range, (60
to 80) kJ mol
-1
. The average activation
energy value of 100 kJmol
-1
implies a
rule of thumb: double the lifetime for
each 5C drop, so 70 kJmol
-1
implies
7C. A theoretical derivation from
transition state theory suggests that
these approximate rules are predict-
able and, hence, universal for materi-
als in museums with chemical instabil-
ity problems. The available data on
relative humidity dependence
suggests that half the relative humidity
will more than double lifetimes for
acid hydrolysis.
Hence, the title of this article holds
generally for museums. A graph of
constant lifetimes on the psychro-
metric chart is presented.
Keywords
Arrhenius, chemical decay, relative
humidity, temperature, deterioration,
psychrometric chart
Double the life for each five-degree drop, more than double
the life for each halving of relative humidity
Stefan Michalski
Canadian Conservation Institute
1030 Innes Road
Ottawa, Ontario K1A 0M5, Canada
E-mail: stefan_michalski@pch.gc.ca
PUBLISHED IN THE 13TH TRIENNIAL MEETING RIO DE JANEIRO PREPRINTS
VOL I Preventive conservation 67
By making equations 2 and 3 equal, and recognizing that e=2.718=2^1.44:
(4) 1.44([1/T
2
1/T
1
]E
a
/R)=([T
1
T
2
]/T
d
)
(5) T
d
=R(T
1
T
2
)/E
a
Selecting room temperature (20C, 293K) as reference temperature for T
1
, and
assuming T
2
is not far from ~293K, one obtains a very convenient approximation
(k is used here as abbreviation for 1000):
(6) T
d
~500k/E
a
Thus, for example, a value for E
a
of 100 kJmol
-1
would give rise to T
d
=5C. This
rule does lose precision as the temperature moves away from 20C, because it fixes
T
2
~293K in equation 5. For the current example, a 10C drop predicts a 4
lifetime, which is close to the Arrhenius prediction, but for a 20C drop, the rule
gives only 16, compared to 20 for Arrhenius. The error, however, is conserva-
tive as a preservation prediction.
A proposed relation for relative humidity and chemical ageing
To make the dependence of chemical ageing rates on RH fit, some authors have
used an analogous exponential relationship to the Arrhenius equation:
(7) ke^(RH)
As will be described in the section on data review, the author has found a power
law relation fits the available data better, and is in keeping with the general
dependence of the chemical reaction rate on a power law of the concentration of
reactants:
(8) k(RH)^n
Between 50%RH and 20%RH, the two equations are very similar, but from
20%RH to 0%RH, they differ radically. The exponential equation typically
predicts degradation at 0%RH that is not much slower than that at 20%RH,
whereas the power law yields zero degradation at 0%RH. This would make sense
for the most important RH-dependent reaction in unstable museum materials: acid
hydrolysis.
Brief review of temperature and RH data on ageing
Paper ageing studies
Robersons (1981) review of 25 paper-fold endurance studies found most E
a
in the
range (97 to 114) kJmol
-1
. In establishing his isoperm diagram for paper ageing,
Seberra (1994) chose ~100 kJmol
-1
. Nishimura (1996) reviewed 27 studies from
three authors: (80 to147) kJmol
-1
, all but 6 within (80 to120) kJmol
-1
. The largest
study of both temperature and RH effects in paper is Graminski et al. (1978). My
re-analysis of their raw data on fibre strength and log-fold endurance loss yields
121 kJmol
-1
and a humidity dependence proportional to RH
1.3
. Yellowing
(concentration of colorant obtained by Kubelka-Munk conversion of the reflect-
ance data) fits 120 kJmol
-1
and RH
1.7
. The Graminski et al. study is very important
because it contains the only data available at several low RH values approaching
almost zero (75%, 50%, 25%, 10%, and 10.5%: the nominally 0%RH value
is a deduction I made based on the original description of the experimental
method, since it is significant to a power law fit). Within experimental error, the
power law, not an exponential law, holds. In their clarification of the role of RH
in changing reactions that produce soluble by-products during accelerated ageing
of cellulose, Erhardt and Mecklenburg (1995) found a power law fits best, with
RH exponents of 2.1 to 3.1. The E
a
range was (88 to 122) kJmol
-1
.
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ICOM COMMITTEE FOR CONSERVATION, 2002 VOL I
Film ageing studies
Nishimura (1996) reviewed 11 studies on dark fading of cyan in colour prints and
films: (80 to117) kJmol
-1
. Lavedrine (1996) reviewed 13 studies of cyan or yellow
fading in colour films: (83 to114) kJmol
-1
. In the Image Permanence Institutes data
(Nishimura 1996), which underlie the important IPI Storage Guide for Acetate Film
(Image Permanence Institute 1993), the values derived for the calculations over the
four humidities tested are (84 to 92) kJmol
-1
. A plot of rates at 21C for various
RH levels (80%, 60%, 50% and 20%) can be fitted well to a power law of RH
1.2
for first-stage hydrolysis. (The Image Permanence Institute chose to fit an
exponential equation, but since its data did not go below 20%RH, either equation
would fit the data without significant discrepancy.) After two decades of routine
film product testing, the director of the Image Permanence Institute (Reilly 1994)
concluded that any future measurements of activation energies of film would
remain in this range.
Magnetic media ageing studies
For magnetic media (audio tape, video tape, computer tapes and diskettes), it is
widely agreed that the primary cause of short life is hydrolysis of the polyester-
polyurethane binder that holds the magnetic particles. Twenty years ago, it had
been shown in the polymer literature by molecular weight and acid measurements
that this binder degraded by acid-catalyzed hydrolysis, that the activation energy
was in the range (68 to 83) kJmol
-1
, that oxygen was irrelevant and that, within a
margin of error, the rate fell to zero at 0%RH (Brown et al. 1980). Cuddihy (1980)
measured the fraction of extractable material in the binder, and proposed a model
with forward and reverse processes. The forward rate was dependent on a steady
supply of humidity; the reverse rate was independent of humidity. Both were
independent of oxygen. By plotting the initial slopes of the curves (at 0%, 11%, 30%
and 100%RH, with and without oxygen), and assuming a power law, I fit a
forward reaction rate that varies as RH
1.4
. Later, Bertram and Cuddihy (1982) used
the same data to fit 59 kJmol
-1
for the forward reaction. Van Bogart (1994)
measured extractables in ageing tapes. I re-analysed the data and deduced that the
forward hydrolysis rate fits a power law of RH
1.3
.
Varnish ageing studies
In a review of the published data on yellowing of the natural resin damar in
various thermal studies, Michalski (1990) derived activation energy of (63 to 70)
kJ mol
-1
from data by Lafontaine (1979) and ~60 kJmol
-1
from data by de la Rie
(1988). The Lafontaine study is valuable since the data predictions published
were later confirmed by measurements after many years of natural ageing at
room temperature at the authors institute.
Summary of the ageing data
Conservation studies of thermal ageing tend to focus on archival materials that are
degrading noticeably within one human lifetime. More than three quarters of all
the studies of paper degradation, acetate film degradation and dark fading of dyes
surveyed found an activation energy in the range (80 to 120) kJmol
-1
. This suggests
a typical value of 100 kJmol
-1
and a doubling of lifetime for each temperature drop
of 5C. For magnetic media binder, and for yellowing of natural resins, the
activation energies fall in a lower range, (60 to 80) kJmol
-1
. This suggests a rule of
doubling each 7C. For dependence on RH, a power law index of 1.3 has been
found to fit much of the available data reasonably well, or is conservative for data
suggesting a higher index. This suggests a conservatively expressed rule of more
than double the lifetime for each halving of RH.
Derivation of the temperature rule from fundamental constants
As summarized by the Encyclopedia Britannica (1999):
VOL I Preventive conservation 69
The Arrhenius equation was originally formulated by J.J. Hood on the basis of
studies of the variation of rate constants of some reactions with temperature.
The Swedish chemist Svante Arrhenius, for whom the equation is named,
showed that the relationship is applicable to almost all kinds of reactions. He
also provided a theoretical basis for the equation by an analogy with the
expression for the thermodynamic equilibrium constant. Later, the numerical
constants A and E were shown by the collision and transition-state theories of
chemical reactions to represent quantities indicative of the fundamental process
of chemical reactions; i.e., E represents the energy of activation, and A
represents the frequency at which atoms and molecules collide in a way that
leads to reaction.
The fundamental chemical reaction types are unimolecular and bimolecular.
Reactions in which three (let alone more) molecules collide for the activated state
are very rare. Chemical deterioration of materials may involve exceedingly
complex reactions, with first order or second order or other observed rates, but
these are simply arrays of predominantly bimolecular reactions. Transition state
theory gives an equation for a bimolecular reaction rate in which one finds the
fundamental constants that underlie the empirical frequency parameter A in the
Arrhenius equation (Dickerson et al. 1970: 798799), as follows:
(9) k=(RT/Nh)e^(S/R)e^-(H/RT)
: probability that breakdown is to products, not reactants; non-dimensional;
estimated for most reactions as between 0.5 and 1
N: Avogadros number (6.0221367 10
23
)
h: Plancks constant (6.626 10
-34
Js)
S: change in entropy, J mol
-1
K
-1
H: enthalpy of activation, similar to the activation energy E
a
, Jmol
-1
In the range of room temperature (20C, 293K), the first few terms reduce as
follows:
(10) (RT/Nh)~(3 to 6) 10
12
s
-1
~10
12.5
s
-1
A range of 50C around room temperature will alter this value by less than 20%.
From Perrys Chemical Engineers Handbook (1984: 446), for a wide variety of
reactions, the term A has been determined experimentally as ranging from:
(11)A~(10
8
to 10
16
)s
-1
(12)logA~8 to 16
This large variation in A is due to variation in the entropy terms, e^(S/R) that
is, log(e^(S/R)) varies typically eight orders of magnitude, between about
4 and +4.
Rearranging the Arrhenius equation to solve for E
a
gives the following:
(13)E
a
=RTln(A/k)
(14)E
a
=5.610
3
(log Alog k)
One now can derive an estimate of E
a
based simply on the order of magnitude of
the rate of reaction, k. Since the time for completion of the reaction is on the order
of 1/k, consider two extremes: reactions that proceed quickly, but not explosively,
in the laboratory (i.e. 1/k~1s) and those that proceed to completion in a museum
over the course of 30 years (i.e. 1/k~10
9
s).
In the lab, log k~0, so (logAlogk)~(8 to 16):
(15)E
a
~(45 to 90)kJmol
-1
(16)T
d
~(6 to 11)C
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ICOM COMMITTEE FOR CONSERVATION, 2002 VOL I
In the museum, logk~9, so (logAlogk)~(17 to 25):
(17) E
a
~(95 to 140)kJmol
-1
(18) T
d
~(3.6 to 5.3)C
Thus, one has derived the old laboratory adage about reaction rates doubling
approximately every 10C, as well as establishing that the identical fundamental
parameters that give rise to that rule also give rise to a museum rule of 5C. The
eight orders of magnitude range in A due to the entropy term S gives rise to only
a 50% range in the estimates of E
a
and T
d
for the museum. Thus, one can argue
that the 5C rule emerges from fundamental constants of nature (R, N and h) and
the fact that the relevant reactions must occur over several decades not much
quicker, not much slower.
The data cited earlier for unstable museum materials show some E
a
values outside
the estimates derived above. In particular, considerable data tend to fall below the
lower estimate of 95. Aside from the possibility that the entropy values fall outside
the range used, it may simply be a reflection of the lower stability of the material.
Materials less stable than the 30-year estimate, such as some magnetic media, will
tend towards the general laboratory rule of 10C. As will be shown in the next
section, degradation mechanisms dependent on permeability or diffusion may also
show lower activation energies.
Activation energies and permeability
Some degradation mechanisms are rate controlled by the permeability of gaseous
reactants. For example, the rapid degradation of some compact discs may be due
to corrosion of the thin aluminium layer, attacked by pollutant gases that must pass
through the protective lacquer coating. For the effect of temperature on such
permeability, one can speculate using the energy of activation of permeability. The
E
p
of oxygen and important pollutants such as SO
2
and H
2
S, varies from about 20
kJmol
-1
for cellulose acetate to about 50 kJmol
-1
for amorphous polyester (Pauly
1989). Thus, diffusion controlled deterioration in general will tend to lower
apparent activation energy, and to a doubling rule for temperature of closer to
10C, rather than 5C.
Conclusions
Conference proceedings with articles that apply the Arrhenius equation to
predictions of lifetime invariably provoke cautionary articles about the serious
flaws in the method. Accelerated ageing is at best a euphemism, and at worst a
delusion, for what common sense tells us is simply baking. Chemistry of degrada-
tion is invariably complex, and extrapolations will be faulty if the rate-determining
step in a chain of reactions were to change with temperature or RH. Attempts by
industry to use Arrhenius to rank commercial products in a very rapid test are
doomed. This article, however, is not about precise application of Arrhenius to a
narrow range of materials; it is about a rough approximation that has a very wide
application to preservation, and very practical implications.
Things in museums that suffer from inherent chemical decay can be assumed to
last approximately twice as long for each 5C drop in storage temperature.
Conversely, things age twice as fast for each 5C rise, so in a sub-tropical gallery
at 30C, as compared to 20C, picture varnishes yellow almost four times as fast,
linen weakens four times as fast, and weighted silk decays four times as fast.
(Sometimes this will be inaccurate, a rule of 7 might be more accurate, or even
10C when diffusion is suspected to be rate-determining.)
Organic materials suspected of suffering acid hydrolysis, such as paper, film and
textiles acidified by pollution, can be expected to last more than twice as long at
35%RH as compared to 70%RH, and much more than four times as long at
18%RH.
Given the practical interaction of temperature and RH, a psychrometric chart
with lines of constant lifetime (isoperms) has been developed by the author
VOL I Preventive conservation 71
(Figure 1). This has been published elsewhere (Michalski 2000) but is offered here
since it is the best currently available representation of the combined role of RH
and temperature in the preservation of chemically unstable materials. It allows the
conservator and engineer to plot regions of operation, cost and lifetime in one
place. Other graphs showing the effects due to time out of cold storage and time
in hot conditions are given in Michalski (2000), along with all the equations
necessary for all figures. To take the sub-tropical example again, looking at the
uppermost edge of Figure 1, materials at 70%RH and 27C will last about one
quarter as long as compared to materials at 50%RH and 20C.
Since the isoperms in Figure 1 are not horizontal lines, it is clear that moving
horizontally to the left on the chart will make things last longer, until one hits the
danger zone for mould, 75%RH or above. This is predictable given the three rules
of thumb involved: double the life for each 5C drop, but double the RH for each
10C drop (assuming no change in air moisture content), with a consequent
halving of life for doubling RH. So the gain in lifetime due to dropping 5C
outweighs the loss due to the consequent increase in RH. On the other hand, this
tendency must never be used to risk damp conditions, since most chemically
unstable materials are very vulnerable to damp. If the chemical decay has a rule for
doubling that approaches 10C, then the two effects would cancel each other, and
isoperms would become almost horizontal lines.
TEMPERATURE C
20 -15 -10 -5 0 5 10 15 20 25 30
H
U
M
I
D
I
T
Y


R
A
T
I
O


g

m
o
i
s
t
u
r
e


p
e
r


k
g


d
r
y

a
i
r
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
x
2

(
x
1
.
4
)
x
1
/
2
x
5
(
x
2
.2
)
x2
0 (x
4.5)
x
1
0
(x
3
.1
)
x
1
9
0
%
8
0
%
7
0
%
6
0
%
4
0
%
3
0
%
2
0
%
1
0
%
x50 (x7)
1
0
0
%

R
H
5
0
%

R
H
5%
x
1
0
0

(
x
1
0
)
x
2
0
0

(
x
1
4
)
15
10
5
0
-5
-10
20
D
E
W
P
O
I
N
T
-15
x
5
0
0

(
x
2
2
)
x
1
/
4
0% RH
x
3

(
x
1
.
7
)
Figure 1. Lines of constant lifetime (isoperms) relative to 20C and 50%RH, plotted on the
psychrometric chart. The isoperms shown are based on the middle value of activation energy
derived from the data review (100 kJmol
-1
), and are thus best representative of deterioration in
paper and film and dyes. (Values in brackets are based on the lower extreme in reported
activation energy (60 kJmol
-1
), and are thus best representative of the decay of magnetic media
binders, and varnish yellowing. The shape of the isoperm lines is only accurate near
50%RH.) The dotted line is a line of constant EMC (equilibrium moisture content) that
averages the corrections published for wood, paper and gelatin (i.e. a correction of 0.4% RH
per degree Celcius). It indicates the correction in RH necessary in cold storage to maintain
constant EMC.
72
ICOM COMMITTEE FOR CONSERVATION, 2002 VOL I
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