Indoor Air - 2022 - Salthammer - Temperature and Indoor Environments - En.ar - En.ar

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2021Received: 10 December | 2022Revised: 20 February | 2022Accepted: 13 March

DOI: 10.1111/ina.13022
REVIEW
Temperature and indoor environments
Tunga Salthammer1 |Glenn C. Morrison 2
1WKI, Braunschweig, Germany

and Indoor Chemistry, Fraunhofer Abstract
Department of Material Analysis
to the changes to be expected as a result of global emergencies such as climate change.
2at Chapel Hill, Chapel Hill, North Carolina, USA
and Engineering, Gillings School of Global
chemistry. Finally, we assess the need to consider temperature holistically with regard
Public Health, University of North Carolina and their distribution in the various interior compartments as well as aspects of indoor
Environmental Sciences
in buildings, the temperature-dependent release of indoor pollutants from materials
Correspondence thermal environment. An extensive literature study is devoted to the thermal conditions
WKI, Department of Material Analysis54
Indoor Chemistry, Bienroder Weg
on typical indoor processes. Then, we describe the heat balance of people in their
E, 38108 Braunschweig, Germany. and start with a review of fundamental thermodynamic variables and discuss their influence
Tunga Salthammer, Fraunhofer
Email:[email protected]. de
rarely including the impact of temperature on indoor contaminant levels. In our article, we
driven, requiring an appropriate energy balance, sometimes considering ventilation but
Funding information
of houses, apartments, commercial buildings, and schools is generally utility and comfort
Alfred P. Sloan Foundation space with the ambient environment, which can vary greatly by region and season. Design
must be adapted so that they feel comfortable. This includes the interaction of the living
is usually accomplished by wearing appropriate clothing, but also the surroundings
to create thermal conditions that serve to maintain their core body temperature, which
further influenced by the thermal comfort needs of occupants. Not only do occupants have
relationships that require a more empirical approach. Indoor environmental conditions are
rates or dynamic air concentrations, can be the result of complex temperature-dependent
composition of indoor materials. Consequently, emergent phenomena, such as emission
temperature, momentum, and pressure gradients as well as by the density, porosity, and
temperature range. On the contrary, transport processes are more influenced by spatial
to have non-linear, very steep changes in chemical phenomena over a relatively small
are proportional to the reciprocal of the absolute temperature. It is therefore possible
- dependent. For example, the logarithm of reaction rate and equilibria constants
as diffusion, partitioning equilibria, and chemical reactions, are predictably temperature
environment is not an ideal system, fundamental physical and chemical processes, such
of an ideal gas is given by the velocity distribution of the molecules. While the indoor
can be assigned to each black body via its radiation spectrum, and the temperature
term temperature is clearly defined for ideal physical systems: A unique temperature
From the thermodynamic perspective, the
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60of 2 SALTHAMMERAnd MORRISOn
KEYWORDS
buildings, chemical reactions, exposure, human perception, partitioning, Thermodynamics
1|INTRODUCTION
Practical Implications
equilibrium and thus to the thermodynamic definition of temperature.
but must be applied with care and with consideration
and coolness. You will rarely get a response that relates to thermal
complex, emergent phenomena (e.g., emission
them, they will probably associate this question with a feeling of warmth
rates) that often require a more empirical approach. of
If you ask someone what the term "temperature" means to
of indoor environments yields useful relationships
the fundamental thermodynamic relationship between free energy (
• Fundamental thermodynamic analysis
temperature, energy, and entropy. Finally, it was Gibbs who derived
have been observed and are expected thermodynamically.
that Clausius recognized the relationship between the state variables
of indoor temperatures, large changes in emission
1865- Lussac, Mayer, and Thompson (later Lord Kelvin). It was around
rates, partitioning, and certain chemical reactions
th century, particularly through the work of Carnot, Gay19first half of the
• Over typical ranges
th century. The beginnings of thermodynamics date back to the17early
in heated or cooled microenvironments would be valuable.
The temperature has been reliably measurable since theG), enthalpy (H
of the temperatures of indoor surfaces and
), and entropy (S) with dG d =H -T ·dS.
not well represented. In all regions, more measurements
the same time as Clausius described entropy, Max von Pettenkofer
measurements of indoor air temperatures are available
Around1of the human body, particularly through the work of Ole Fanger.
across many parts of the world, but many regions are
“Thermal Comfort” established itself to describe the overall heat balance
• Good seasonal and daily
form the basis for the well-known comfort diagrams. Finally, the term
substantially. attention, especially for poorly insulated buildings where
developed the temperature–humidity diagrams named after him, which
microenvironmental temperatures can vary
ventilation and heating technology. A few years later Richard Mollier
on exposure to chemical pollutants deserves more
th century, Herrmann Rietschel founded modern19the end of the
• The influence of indoor air and surface temperatures
or negative effects the indoor climate can have on human health. Toward
indoor hygiene and thermal comfort. Pettenkofer showed what positive
on the physiology of people indoors and thus created the basis of modern
examined the influence of temperature, humidity, and air exchange2
is calculated from the air temperature and the mean radiant temperature. 1 m 1heat and moisture reservoirs. The specific heat capacity of
required the introduction of the operative temperature, which building materials represent3kg of wood or wood-based products.
of temperature was not sufficient to assess thermal comfort. This of air is about half that of
their well-being. Interestingly, the original thermodynamic definition release of a molecule from a material or product.
primarily impact the physiology of humans and thus partly determine indoors, starting with the diffusion-controlled or evaporationcontrolled
like temperature, humidity, air speed, clothing, and physical activity Temperature-dependent mass transfer and reactions are common5
It was found that thermal factors interaction processes with particles and other surfaces take place (see
theory, in liquids the law of Stokes-Einstein applies. Furthermore, various
temperatures by behavioral adjustment, physiological air humidity of The diffusion coefficient in air follows directly from the kinetic gas1Figure
psychological habituation or expectation. able to adapt absorption kinetics, which are related to the saturation vapor pressure (
60% as comfortable. However, humans are also–40%acclimatization, and ). As a rule, these are reversible adsorption andP*/air partition coefficient (
with a relative Standard –20find an indoor temperature range of ) or the octanolKOAand mass as well as on the flow conditions in the room.
period of time, do not result in appreciable heat loss, since 3 5523°C ) of a molecule. The dynamics of the particles in turn depend on their size
for a short4People who live in temperate climate zones generally

ASHRAE equilibrium. However, activities, such as opening windows ester hydrolysis. In contrast, the hydrolysis reaction catalyzed by H
therefore not realistic. In practice, of course, residents need fresh of Arrhenius or Eyring. An important reaction in the interior is alkaline
nonair, sun, wind, and rain also contribute to an exchange of energy are usually bimolecular and often follow the temperature laws
and mass with the environment, which keeps the system in can take place in the condensed phase or in the gas phase. These
without any air exchange shielded from all external influences Homogeneous chemical reactions3O+on surfaces, there are two common
such as wind and solar radiation is an adiabatic system and house been examined particularly well. For heterogeneous reactions
82 a thermodynamic point of view, a perfectly thermally insulated ozone, which are long-known from outdoor atmospheric chemistry, have
°F (19.4–27.8°C) for thermal comfort purposes of occupants. From the indoor environment, gas-phase reactions between monoterpenes and
°F and67therefore specifies a range between approximately ions is only of minor importance here. In
| 60of 3
SALTHAMMERAnd MORRISOn
Liquid particle
Heat an d mass
xch angee
Solid particle Gas phase reaction
Deposition into
house dust
Diffusion in air
Heat and mass

ex change
Surface reaction
Diffusion in liquid and solid
H2O Hydrolysis H2O
1F I G U R E Dynamics and reactions of a chemical compound ( ) in the indoor environment
sufficient if only one reaction partner interacts with the surface (see products, the more the equilibrium shifts to the side with the lowerΔG 0
is mechanisms. According to Langmuir-Hinshelwood, reaction partners The relationship between .GΔ0the absolute temperature ,Tis given by
have to interact with the surface. According to Rideal-Eley, it , and the dimensionless equilibrium constantequation (2).
1Figure).
( )
to the kinetics of irreversible reactions. In general, the rate ratio ( K 1 1
n2∼ Δ G0 ∙ − (2)
to the evaporation of molecules from a solid or liquid phase and K1 T1 T2
increases. This applies reaction between two temperatures
The rates of most chemicalk2/k1processes increase as the temperature for describing the experimental observations of pollutant
) of aT1and T2can be expressed by equation (1).6 concentrations in houses and test chambers were developed. models
experimentation. With the increasing availability of powerful
( )
k 1 1 computers and user-friendly software, the first diffusion-based through
n2 ∼ − (1)
k1 T1 T2 s, indoor-related sciences proceeded primarily1990the
chemical phenomena observed indoors, but the mechanisms driving
be derived from the van't Hoff rule. Finlayson-Pitts and Pitts emergent phenomena such as emission rates are complex. Until
rule applies to many simple reactions in a limited temperature These fundamental relationships should influence8–10data points.
range, provided that the free enthalpy of reaction is independent Hoff increasingly complex models were interpreted with only a few
of temperature. Under no circumstances may general validity of indoor sources was rarely taken into account at this time.11
fugacity, activity, vapor pressure, partition coefficients, and emission This initially led to the problem of over-parameterization, since behavior
rates are similarly influenced by temperature. This so-called van't emission models, included temperature considerations. 12
rate doubles or quadruples when the 10temperature is increased by on the emission wall paints led to the development of mechanistic
K. However, other parameters like condensed phase the reaction Studies on PVC coverings and13The influence of temperature and humidity
found by van't Hoff that for many chemical reactions in the formaldehyde14in the material is also temperature-dependent.
It was empirically7that deviations from the proportionality given by which later more complicated, since the concentration of free
point outequation (1reactions, or reactions with prior equilibrium. of the emission behavior from wood-based materials is even
in many atmospheric reactions. The same applies to other complex The theoretical description15
reaction types such as enzyme kinetics, catalysis, heterogeneous conditions. The distribution of indoor air pollutants in dependence
) can be observed6 transport in components and houses, especially under extreme weather
The chemical equilibrium constantK Gibbs free energy is is challenging in light of climate-dependent heat and moisture
is also dependent on the temperature. At equilibrium, theG Δenergy = of field measurements. Predicting the future of building environments
of Le Chatelier, the greater the difference in the Gibbs standard free vary greatly in space and over time, further complicating interpretation
According to the principle .0GΔ0between educts and Environmental conditions in buildings may
|
for temperature and humidity gradients as well as air flows is also a field they collide with one another. From the statistical description
frequent theoretical studies. Overall, the importance of models of the velocity distribution according to Maxwell-Boltzmann, when
the characterization of indoor air quality has increased significantly. of on a container wall is a result of the individual molecular collisions on
of the walls. The molecules do not have a uniform velocity, but rather
their impact on indoor environments, comfort, and exposure. a velocity distribution since they transmit energy and momentum
values regionally, seasonally, and within microenvironments. We through the kinetic theory of gases. The pressure that a gas exerts
then discuss important temperature-dependent processes and 1860of temperature was given by Maxwell and Boltzmann in
relationship to the relative air humidity and its measured description gas constant, and equation (4of the molecule ensemble
selected thermodynamic concepts, the drivers of temperature, the ) follows for the mean square of the velocityu2.R The microscopic
It is the aim of this article to characterize temperature, in is the idealMW is the molecular weight of the substance.
a very broad sense, in indoor environments. We review
3∙R ∙T
u2 = (4)
MW
2| THE THERMAL ENVI RONMENT Equation(4of an ideal gas to the temperature. Furthermore,
) directly relates the velocity of moleculesequation (5gas pressure
2.1| Temperature: A thermodynamic state variable m ) for the relationship between thep from the kinetic gas theory.
and the mean square velocity can be derivedV is the volume, and
book "The Second Law." resulted in an intersection at approximately of an individual molecule multiplied by the number of molecules).
to low temperatures16temperature is nicely told in PeterW. Atkins is the mass of all molecules (mass
The scientific history of the straight lines obtained at different pressures
linearly with temperature at constant pressure. The extrapolation of m∙u 2
= (5)
properties of gases and found that the volume of a gas changes 3∙V
- Lussac (1808) investigated the temperaturedependent
Gay fixed points. After determining the temperature scale based on the The combination ofequations (4) and (5) and transformation of Vin
freezing point and the boiling point of water by Celsius (1742), resultequation (6), which is known as the ideal gas law.
uses a cold mixture, freezing water, and body temperature as In

m
in a reaction system can decrease. The consumption,1714 ∙V = ∙R ∙T =n ∙R ∙T (6)
MW
is overcompensated by the gain in entropy, so that the temperature
Fahrenheit introduced the scale named after him, which of thermal energy from volume-related concentrations according to n =m volume (
different starting temperatures is not to be attributed to the can be converted intoVmThe molar amount of a substance results
difference but to the resulting increase of entropy. This and with /MW. With the molar and temperature, massrelated concentrations
particularly important for understanding why endothermic temperature ) at a certain pressureequation (7).
processes can occur spontaneously, or in other words, why is
] [g ]V (p,T )
m
scale introduced later by Thompson. Another absolute zero. = ppb ∙ (7)
m3 MW
came from the relationship between temperature absolute temperature
a thermodynamic point of view, the temperature important finding and gaseous air constituents can be treated as ideal gases.
of two bodies in thermal contact with each other and entropy. From Under environmental conditions, air
can also be explained, since for ideally crystalline273 −G Δequalization
disappears when the temperature approaches temperature scale
°C. This observation formed the basis for the systems the entropy 2.2|Absolute and relative humidity
nd law of thermodynamics, the absolute2the help of the
becomes negative. With the air pressure in dependence of height and temperature lapse rate.
nd law, Kelvin is today defined by the Boltzmann constant2of the with increasing altitude. Different equations are available for calculating
the base unit Kelvin (K). Deviating from the original and meter. of the air that envelopes the globe creates an air pressure that decreases
interpretation of a Carnot heat engine by use variable with The effect of gravity on the mass7The standard pressure at sea level is
∗
to the base units kilogram, secondkB = 1.380649·10−23thermodynamic airPa. The mass of water vapor contained in the air 101325 =
The temperature is an intensive state J/K and therefore directly related contributes to this pressure as the water vapor partial pressureH2O
humidity
17temperature. The conversion to °C is calculated according to
air is limited depending on the temperature and reaches its highest value
point of water was the reference value for determining the absolute air with the water vapor saturation pressure. The gaseous state of matter
is then in equilibrium with the solid or liquid phase. The absolute
the triple ,2019Until equation (3). The intake capacity of water in .H2O is calculated by
[][]
◦C = T K −273.15 (3) transformingequations (7)into (8).
| 60of 5
Temperature (°C)
mH2O p2H O ∙MW H O2
H2O = = (8)
V R∙T
the percentage ratio between the actual water vapor partial pressure
The relative air humidity RH is H2O and the water vapor satura-
∗
tion pressure
H2O
over a flat water surface.
Relative humidity (%)
pH2O
H(%) = ∙100 (9) 2U R E I G F Equilibrium moisture content of wood (labeled
PH∗ 2O
of relative air humidity and temperature. The figure was
adapted from the Forest Products Laboratory Wood Handbook. function
contours, in %) as a24The yellow dots (15°C, 80% RH ; 23°C, 50%
very differently in different climatic zones, but most people perceive
RH°C, 34% 30 ,RHg/m³ 10.28the same absolute humidity of
relative humidity <40% as unpleasant. Air that is too dry is often
) represent
associated with sensory irritation in eyes and upper airways. a
Temperatures and humidity are perceived18–20 the wood for moisture at the higher temperature. The yellow dots in
condenses. At a temperature of 18.35air can absorb a maximum of content of wood, assuming that RH remains unchanged. At
falls below RH = 21g/m³ water vapor. With the dew point and water RH, the higher temperature results in a higher moisture moisture
,50%°C, dry water vapor saturated air cools down, the temperature content in air; this, in turn, is balanced by a reduced affinity of the same
electrical properties. Tair the dew point according to the Magnus equation between approximately same absolute humidity of 30°C and 15
°C and21 =21When material surfaces depends on their influence on the equilibrium temperature in the indoor-relevant range
with hydrophilic materials, on the contrary, equilibrate slowly. With seen that the 2Figure g/m³ (50% 10.28°C has only a minor
1.85Debye, water molecules are strong dipoles, so the interaction show the equilibrium moisture content for theRH values in
hydrophobic building materials equilibrate quickly, while fine-pored relatively small temperature range. For most practical purposes, the
in the room and the humidity often determine is balanced. Künzel the same absolute humidity, moisture content varies greatly over a
of the building materials. Coarse-pored and with the materials °C) under different conditions; this demonstrates that, for to 23at 2
°C. Water molecules in the air exchange10.2is 22the water content added Figuremay be applied to wood of any species.24g/g) for water, 0.4
23in the material or on the material surface and in the environment m by in which substances can be adsorbed and can be specifically
The exchange takes place until the water vapor partial pressure (up to plasters. The adsorption/desorption equilibrium is influenced
of 4h. Assuming a space of 12g of water per square meter within 50 – the temperature. Many zeolites have a high absorption capacity
40°C. Under these conditions, plaster absorbs20at a temperature are aluminosilicates with a structure of uniform pores
80%to 40%wall coatings by increasing the relative humidity from to a decrease in humidity. Wood therefore functions as a compensating
m ×measured the water absorption capacity of various 5by Künzel, × buffer for the moisture content of the room air and is comparable
to remove water from air. According to the measurements other moisture-dynamic building materials such as plaster. Zeolites
the highest capacity. Therefore, short-term ventilation is inadequate the increase in humidity. If, on the contrary, the air is too dry, then
g of water. The water absorption capacity of textile floor coverings wood releases water molecules into the room air and acts against
is of the same order of magnitude as that of plaster, and clay has are sorbed by an open-pored wood surface, which dampens
of 865°C, 50 m³ of air can absorb a maximum of20g. At 1800 humidity in a room. In a humid atmosphere, water molecules is less than
means a water buffer capacity of approximately doors, a wall area A material like wood thus has a stabilizing effect on25 .1%the air
m² can be calculated. Without taking the floor 40into account, this climate. In have a certain buffer capacity with regard to air humidity.
m³ and considering windows and 50m = 2.523adsorption process. of a gypsum board is why they are also used to regulate the indoor room
the water desorption process takes longer than the formation of microorganisms. 26contrast, the equilibrium moisture content
damage the building structure through drying out, swelling27which or the
.15%–10%materials have a moisture balance of approximately Porous materials therefore high can
and humidity, wood, wood-based materials, and other organic building heritage, especially churches, where28fluctuations (see Section
Over a wide range of indoor temperature 2Figure of lignin. It can be results in large temperature and humidity well-known problem in cultural
the ability of the walls to take up water is also limited by the presence Air humidity that is too low or too poor climate control often
them hygroscopic. Therefore, wood has a great affinity for water, but This is a7.4).29
cells are largely made of celluloses and hemicelluloses, which make Duncan et al.30information seeNazaroff and Weschler,
humidity at which the wood is neither gaining nor losing moisture. Wood on surfaces. Formore of indoor air, surface, and material moisture.
equilibrium moisture content of wood for different temperatures and point out that many31types of indoor aqueous chemistrymay occur
shows the calculated who provide a detailed analysis
|
3|C S OF CHEMI CAL PROPERTI ES

THE THERMODYNAMI
3.1|pressure and the Clausius–Clapeyron equation

∆vapH
R
melting point
Vapor
ln P
subcooled liquid
dependence of the vapor pressure∗is expressed by the Clapeyron P∗L
The saturation vapor pressure temperature. The temperature ∆sublH

R
sublimate into the gas phase of the atmosphere and determines
solid
P∗S
the maximum concentration in equilibrium at the respective or
of a substance indicates its tendency to evaporateequation (10).
dP ΔpSva ΔvapH
= = (10)
dT ΔVm T ∙ ΔV m Tm T
T/1
ΔvapS denotes the change in the molar entropy, ΔVm Δ 3F I G U R E to the vapor pressure of the subcooled liquid
the change in the molar volume during the evaporation process, and to Clausius-Clapeyron with phase transition and extrapolation
vap H is the evaporation enthalpy. ΔvapH of the gas. This simplifies Vapor pressure curves according
as constant over a small temperature range. It can also be assumed

is that the volume of the liquid is negligible compared to the volume Sage.37of these methods is based on the most accurate determination of
is temperature-dependent, but can be regardedequation (10 The reliabilityΔvapHwith decreasing vapor pressure. With EPI Suite
) to the Clausius–Clapeyronequation (11). whereby the inaccuracy increases ,38and SPARC, 39Schwarzenbach et al.,
K was published by 298the vapor pressure of subcooled liquids at

( )
P∗ ΔvapH 1 1 - parameter linear-free energy relationship (LFER) approach to determine
n2 = ∙ − (11)
P1∗ R T1 T2 are available for estimating vapor pressures and other parameters. A poly
program interfaces40the hexadecane/air partition coefficient (see Section

where∗and ∗are the saturation vapor pressures at tempera- - specific parameters like polarizability, donor/acceptor properties and
1 2
turesT1and T2experimentally using the Knudsen effusion method. which requires the input of several molecule3.3of high and low volatility.
substances can be determined determining the vapor pressure. and theoretical vapor pressures have been observed for substances
respectively. The vapor pressures ,32of medium- and low-volatility ). In practice, significant differences between experimental41
OECD guideline lists a total of eight experimental methods for2006 only been published for a few SVOCs. This includes data for hydrocarbons,
Antoine 33techniques via gas chromatography are also common. So far, reliable vapor pressures and enthalpies of vaporization have42
Indirect measurement34The higher temperatures. The empirical polycyclic aromatic hydrocarbons,43carboxylic acid esters, 44–46biphenyls,
from the vapor pressure curve to room temperature (seeequation (12 polychlorinated47polybrominated diphenyl ethers, 48and biocides. 32,49al.
In practice, the measurements are often carried out at extrapolate of vapor pressures using quantum chemical methods. Grimme et
) is then used to3Figure ). A new and promising approach is the prediction50use a
B (12) semi-empirical method for the computation of accurate conformer

ogP =A−
C +T
consideration of solvation models. This made it possible behavior.
3.3to calculate a logarithmic partitioning coefficient (see Section under
A,B , and C are empirical, substance-specific parameters. Antoine ensembles and refinement by density functional theory
coefficients are available for many compounds.35solid is steeper (see K when assuming ideal K is 298Pa at 0.15to a vapor pressure of
problem arises if there is a phase transition when extrapolating to for n-hexadecane in itself, which corresponds 7.77) of 51Pa. 0.20
room temperature. In this case, the vapor pressure of the subcooled A 298The experimental value at52
liquid is obtained and the values are too high. The curve of the
liquid 3Figureof sublimation also contains the enthalpy of melting (Δ
is an essential parameter for es- sublH = ΔvapH + ΔmHof the subcooled 3.2|Chemical fugacity and activity
that ∗). Nevertheless, the vapor pressure
L
of a solid ∗), since the enthalpy
timating gas/particle distributions. Pankow36assumes

L
composition of the system. Gibbs recognized that the chemical potential
better represents the evaporation behavior than the vapor pressure in turn are a function of pressure, temperature, and the chemical
∗.
for a covered particle surface S
is the sum of its intramolecular and intermolecular energies. These
methods for calculating the vapor pressure from theoretical The energy state of a molecule in a mediumµi of a substance i of the molar
approaches are available, which are discussed by Sage and Various in a compartment can be defined by the partial derivative
| 60of 7
free enthalpyGi with respect to the amount of substance ni to

i=Z ∙f i (19)
accordingequation (13).40
( )
Gi The fugacity of a substancei fugacity capacities. This results in
i= (13)
np i,T connected phases at equilibrium is the same. Consequently, the
distribution coefficient is directly obtained from the ratio of the two
Withµi that describes the change in the free energy of substance inequation (20) for a substance i equilibrium conditions.
one has an intensive quantityi quantitatively. Analogously, 2phase that is distributed between air and water (w) under
to 1during the transition from phase µi state of a single phase.
Zi, air H
describes changes in the thermodynamic AW= Ci,air = = (20)
C i ,w Zi,w R∙T
potential depends only on the partial pressure conditions
ideal mixture of gases, the the absolute temperature pichemical
the partial pressure under standard ,pi*For an ideal gas or an KAW is the air/water distribution coefficient, and H note that
and ,T,µ* is the chemical potential at standard conditions. compartments. and Paterson H can be expressed in different units).54
constant (please the distribution of chemicals in environmental
( )
pi to investigate water. The fugacity models by Matoba et al. 55is Henry's
i= ∗ +R ∙T ∙ln (14)
i pi∗ it was Mackay ,1983In 56Mackay later used the term fugacity
to accidentally spilled 222PCBs from fluorescent tubes and Radon-
(15 therefore introduced a correction term for the pressure. In when released from method, they calculated the indoor exposure
Deviations from ideal behavior occur in real gases. Lewisequation of volatile organic compounds in indoor spaces. Using this
θ ,)i denotes the fugacity coefficient and fi is the fugacity. method based on the fugacity concept for estimating the distribution
room temperature57,58and humidity conditions. Bennett and Furtaw
i=i ∙p i (15)
who described a pesticides on floor, wall, and ceiling under various
sprayed and vaporized calculation of reliable fugacity capacities
In real systems, the fugacity replaces the pressure, so that . The problem here is the59aerial concentrations and amounts of
equation(16) can be derived from (14) and (15). describe time-dependent products, walls, ceilings, air exchange, etc.)
(gas phase, particle phase, house dust, building used by Shin et al.
( )
fi the fugacity model for any indoor equilibrium, Zcompartments
i= ∗ +R ∙T ∙ln (16)
i pi∗ framework was later also from the ideal gas law with .60generalized
For the simple case of a gas/particleZair A general indoor fugacity
to liquids and solids. Instead of the partial pressure in the gas phase can be derivedn/V =f /(R·T) =f·Z air.
potential. This definition allows the fugacity concept to be applied
phases then provides information about the change in the chemical

1 (21)
air=R ∙T
and interactions in the system. The comparison of fugacities in different
tendency of a substance from a phase than the sum of the energies For the particle phase, the fugacity coefficientZpart results from
definition of fugacity. He argued that it is easier to look at the escaping equation(22).59
Lewis also presented an illustrativepi, the vapor pressure of component i
related to the vapor pressure of the pure substance. In an ideal solution, KPA ∙part
part=
(22)
in a mixture isequation (17) follows directly from Raoult's law, where xi of R∙T
is the mole fractioni in the mixture.
KPA is the gas/particle distribution coefficient, and ρpart prediction of

i= ∗ +R ∙T ∙ln xi (17)
is the density of the particle. There are several approaches for theKPA.
i
Equation(23) according to Harner and Bidleman61is often used. KOA
law, and the reference fugacity of the pure liquid.xicoefficient is the octanol/air distribution coefficient, andfom_part
the activity ,γiThe fugacity is obtained from the mole fraction is the organic fraction of the aerosol (see also Section4.2).
which describes the deviations from Raoult's ,
ogKPA = logKOA + log fom_part −11.91 (23)
i=i ∙x i ∙pi (18)
Calculation methods forZ the publications by Bennett and Furtaw

The product ofγi and xi is the activity ai of component i concentration can be found in and distribution of chemicals in indoor spaces. 59
in the mixture. The fugacity has a direct relation to theCi predict the transport60values in various other indoor compartments
of a substance in a medium via the proportional constantZcapacity. and Shin et al. model has also been used by other authors to
called fugacity ,53 The fugacity62,63
|
( )
with a few components. It will be shown later that for real Δ 21H 1 1
nK12 (T2ln=)K1 T +
2( 1) ∙ − (25)
systems it is often necessary to derive empirical relationships. systems
R T1 T2
based fugacity considerations are limited to simple
Strictly speaking, thermodynamically mol/(Pa KOW,K OAand ,KAW are correlated with each other via equation (26
). ForR K), Henry's constant =∙J/(mol 8.314H m³).∙in the unit
must be given74
3.3|Partitioning coefficients
K
OA=OW =K OW∙R ∙T ∙H (26)
KAW
Sangster .2and 1partition coefficients for any combination of phases
determination of in the various solutes must also be considered. 64
as well as Leo et al.65In principle, the fugacity concept allows the Based onequation (26), Weschler and Nazaroff75Schwarzenbach
partitioning based on chemical potential and activity. It is important °C. Goss and32gas phase, assuming a skin surface temperature of
to mention that the equations discussed in this section only apply between skinsurface lipids and the /air partition coefficient log
to non-ionizable compounds. In the case of acids and bases, the present a relationship for calculating76the partition coefficient
temperature-dependent dissociation and equilibrium constants calculating the equilibrium partitioning of organic compounds.KHdA (L
offer detailed discussions of the thermodynamics of also discuss the importance of the logarithmic hexadecane in
In practice, the already discussedKAW,K OWand ,KOA air, water, and soil. ) as surrogate for the van-der-Waals term
coefficients essentially determine the distribution and transport between already been discussed and criticized in detail that the published
a chemical has been released into the environment, these insufficient measurement accuracy. For example, it has of magnitude.
are of particular importance. After40with regard to intake and uptake. of distribution coefficients published data increasing as KOW is their
humans, inhalative, oral, and dermal routes are of major importance values for DDT cover several orders77,78The major weakness
of the substance between compartments and subcompartments. In The same applies to SVOCs, with the range ofKOW and KOA
in these organisms are also influenced by the distribution increase.79are often converted into one another from related properties
chemical substances and the bioaccumulation its tendency to bioaccumulate. Partition coefficients80or using equation (26),74
indicator for66,67The octanol/water coefficient KOW exposure of organisms to amplify errors. Quantitative structure–activity relationship (QSAR) models
The preferably in the hydrophilic or lipophilic phase, which is an which can81–83and linear-free energy relationship (LFER) 84compounds.
be used to determine whether a substance accumulates be neglected. At 68 in SPARC and EPI Suite deliver very different results for many
.0.2705octanol is-1K, the molar fraction of water in 298can especially has been shown, however, that QSAR algorithms as implemented
be taken into account that the mutual solubilities are not to towet are also popular approaches for predicting distribution coefficients. It
However, it69Therefore, KOW octanol. The octanol/air coefficient -1must models41Rodgers et al. 85of solvent/solvent or solvent/air phase transfer (
organic compounds (SVOCs). KOA is, inter alia, a predictor of gas/particle70,71 compounds. The authors also present molar internal energies 74for
of organic films on indoor surfaces.72values are usually referred of semi volatile method to calculate accurate values of physicochemical properties
partitioningKOA and gas/settled house dust to describe the growth applied a BayesianΔU°according to van't Hoff's law. Baskaran et al.
air that ranges73from very dry to very humid; therefore, the appropriate can be used to calculate temperature-dependent partition coefficients
is also useful of particles and surface films can be in equilibrium with ), which86present a database of KOA and discuss the applicability of Δ
between wet and dry K OA will depend on RH differences in log compounds 1500values for approximately OAU°et al.
solubilities and negligible donor or acceptor properties, however, the - dependent calculations using DDT as an example. Salthammer
octanol. For molecules with low to moderate water-1The organic fraction values for temperature51compounds using quantum chemical methods.
and lie within the continuumKOA octanol are small.-1for wet and dry organic 67have calculated partition coefficients for
values51 The poly-parameter LFER approach as described by Goss87

K12from the difference between the chemical potentials of substance can then be estimated with the help of quantitative descriptors. Goss
, Δ12G can be calculatedi the distribution coefficient in its logarithmic form. In understanding of the partition process. The interaction energies
It is also common practice to provide .2and 1in phases equation (24) intermolecular interactions comprehensively and provides a mechanistic
idenotes the Gibbs free energy of phase transfer.40 covers relevant87compound between two phases can be described with
showed that the distribution of an organicequation (27).

Z RT∙lnZi,phase_1 −RT ∙lnZi, phase_2 − Δ12Gi
nK12=ln i,phase_1 = − = ogK12 =s ∙Si +a∙Ai +b∙Bi +l ∙Li +v ∙Vi +c (27)
Zi, phase_2 RT RT
(24)
Si,A i,B i,L i,and Vi are compound-specific Abraham descriptors.88

IfK12is known for a certain temperature T1the value of ,K12 Si is the polarizability/dipolarizability), Ai hydrogen bond acidity (donor),
at temperatureT2from the phase transition enthalpy with Δ is theBi is the hydrogen bond basicity (acceptor), Li coefficient log
can be calculatedG = ΔH -T ΔS according to equation (25). is the logarithmic hexadecane/air partitionKHdA ( a surrogate
| 60of 9
Waals term), and McGowan volume Vi is the McGowan volume.89 equation(25),K OA °C. As can be seen from the example of the PCBs in 30to
The sorbent-specific parameterss,a ,b ,l , and v for the van der °C15decrease by about a factor of six for an increase in temperature from
describe the complementary sorbent properties. TheVi will1Table can be predicted more precisely than the absolute values.
be calculated from the molecular structure of the respective target coefficients themselves. This means that the temperature dependencies
compound following a procedure as described by Abraham, and in a similar range and can be determined with higher accuracy than the
canLi can be determined experimentally by gas chromatography.90–92 the respective enthalpies are ,
been developed for compounds with unknown descriptors. to obtain the ultimately used Gibbs free energies. The
Quantitative structure property relationships (QSPRs) have82,93For K is computed—depending on the required accuracy approximation
OWoctanol) and -1(wet KOA been published by Schwarzenbach et al. size of the system—by composite DFT methods, high electronic part
K, poly-parameter (pp) LFER equations have 298octanol) at -1(dry 40 - level hybrid density functionals, or wave function theory. level and
-of-the-art continuum models, accurately account for long-range
ogKOW =2.41∙Vi +0.43∙Li −1.41∙Si −0.18∙Ai −3.45∙Bi +0.34 (28)
dispersion effects and treat thermostatistical contributions state
in the framework of a modified rigid-rotor-harmonicoscillator London
ogKOA =0.07∙Vi +0.90∙Li +0.47∙Si +3.52∙Ai +0.82∙Bi −0.14 (29)
by are computed by efficient semi-empirical quantummechanical and
force-field methods. These calculations include solvation effects
phase transition enthalpies (see partition coefficients.30 low-lying conformers are generated. Potential energy surfaces
equationsand 31), the van't Hoff equation (25With the corresponding structure ensembles consisting of all energetically
) can be used to calculate temperature-dependent limited. But even the properties of complex molecules can now
be reliably calculated with a reasonable amount of effort. Starting is
OWHi = 18.9 ∙V i − 8.3 ∙L i + 5.3 ∙S i − 20.1 ∙A i + 34.3 ∙B i + 1.7 (30)
from an initial three-dimensional input geometry, molecular
to compounds with long alkyl chains, the number of conformers
OAHi = 1.6 ∙V i − 9.7 ∙L i + 6.0 ∙S i − 53.7 ∙A i − 9.2 ∙B i −6.7 (31)
easy, because, in contrast QSAR approaches in the near future.
In general, the theoretical50treatment of PCBs is comparatively
al. years, quantum mechanical calculations for determining distribution that quantum mechanical methods will more and more replace
coefficients have become increasingly popular. Zhou et Consequently, it is to be expected
In recent94developed a method to determine the KOW free energy Δ When calculating gas/particle distributions, substances with mediumK
all G theory (DFT). Solvation models are used to calculate the Gibbs OAor KHdA values cause the biggest problems.79,124Partitioning theory 125
PCB congeners on the basis of density functional 209values of diethyl phthalate (DEP) with log phase. Conversely, tri- 99%that more than
QSAR models perform better than Δ95–99Fu et al. 100methods for phase. For di-KHdA ethylhexyltrimellitate (TOTM) with log -2of a substance like
compared predictionKOA of transfer between two phases. that the gas uncertainties of 6.75 =KHdA ethylhexyl adipate (DEHA) with log -2shows
and come to the conclusionG models. decisive effect on the gas/particle ratio. 99%is more than 18.87 =KHdA is in
the challenges and pitfalls of methods to measure 101–106Leo 107as Klöpffer on the contrary, small ,12.16 =KHdA associated with the particle
as well108Experimental techniques are also applied. discuss have a92
measuring KOWSeveral devices are available to determine .KOA problems concern the interaction of organic compounds with clothing
experimentally.109–111critically column is a common method for Similar126and the sorption of substances through the skin. 127
Gas chromatography on a non-polar capillaryKHdA values.90,91 Equation(24corresponding enthalpy using a pp-LFER approach.
and vice versa. negligible. -1that a certain amount of water is soluble in the the distribution of a substance between any two compartments. The
of n-hexadecane in water and of water in n-hexadecane is69,112octanol air/surface adsorption equilibrium can also be determined from
However, experimental work must take into account solubility ) can be used to calculate128The work by Wei et al. 129
The113Mackay et al. 114–117and measured distribution coefficients. /gas partition coefficients for different SVOCs and sink materials.
provide a comprehensive overview of predicted presents a compilation of publications on measured surface2Table
various methods. There are differences of up to 1Table lists log KOWlog , to partitioning coefficients for various indoor compartments.
KOAin the log 0.6For six polychlorinated biphenyls (PCBs), to contains references
transfer enthalpies, which were calculated or measured according
and phase ,KOW values. Shiu and Mackay,118values. Grimme et al.
tends to lower values for log –0.20literature data, give errors of 4|GAS/PARTI CLE DI STR IBUTION
rigid molecules. The510.50 for their recommended pp-LFER method
who evaluated errors are larger for flexible molecules than for air. If, on the contrary, it is sorbed to particles, it can be deposited in
logarithmic partition coefficients, but also state that the uncertainties form, there is a high probability that it will leave the body with the exhaled
increase with the number of possible conformers, that is, that the particles. If a waterinsoluble atom or small molecule is inhaled in gaseous
for 0.5estimate errors of about KOWThe calculated and measured log . of whether the substance is in gaseous form or whether it is bound to
KOA typical phase-transfer enthalpy (~85 kJ/mol) and applying into the human body, not only is the path important, but also the question
values and the enthalpies for octanol/air agree very well. For For intake of a chemical substance
|
1TA B L E Compilation of experimental and calculated logKOWlog ,KOAand phase transfer enthalpies for six polychlorinated biphenyls ,
(nomenclature of the PCBs according to Ballschmiter and Zell119)
Compound 28PCB- 52PCB- 101PCB- 138PCB- 153PCB- 180PCB-
CAS 7012-37-5 35693-99-3 37680-73-2 35065-28-2 35065-27-1 35065-29-3

1
logKOW 5.80 6.10 6.40 7.00 6.90 6.89
2
logKOW 5.62 6.09 6.50 7.25 7.16 (7.36)
3
logKOW 5.63 5.74 6.26 6.68 6.76 7.18
4
logKOW 5.77 6.20 6.63 7.06 7.06 7.49
5
logKOW 5.42 5.61 6.10 6.67 6.59 7.13
6
logKOW 5.23 5.52 5.84 6.30 6.54 6.89
ΔOWH7( kJ/mol) 19.74 18.63 22.32 27.51 25.97 30.53
8
logKOA 7.92 8.22 9.07 9.81 9.74 10.52
logK 9OA 7.85 8.22 8.73 9.66 9.44 10.16

10
logKOA 7.84 8.14 8.84 9.71 9.54 10.34
logK 6OA 8.03 8.61 9.22 10.07 9.83 10.59
ΔOAH11( kJ/mol) 74.06 75.29 81.16 88.77 86.97 93.84
ΔOAH12( kJ/mol) 83 86 73.54 87.77 89.90 86.83
1Shiu and Mackay (1986) :153PCB- ,138PCB- ,101PCB- ,52PCB- ,28PCB-118Sangster (2016). :180; PCB-120
2Hansch et al. (1995)121listed but not recommended). :180( recommended value. PCB-
3Zhou et al (2005).94
4Ruelle (2000).122
5pp-LFER (28equation ).
6Salthammer et al. (2022).51
8Kömp and McLachlan (1997) :52PCB- ,28PCB-109Harner and Bidleman (1996). :180PCB- ,153PCB- ,138PCB- ,101; PCB-102
9Li et al. (2003)123( evaluation of data, FAV: final adjusted value).
11Kömp and McLachlan (1997) :52PCB- ,28PCB-109Harner and Bidleman (1996). :180PCB- ,153PCB- ,138PCB- ,101; PCB-102
between particles and chemical substances came from Junge Inequation (33),K L is the Langmuir adsorption constant withK L =K BET/
exposure. His aim was to describe the global transport of pesticides.138,139 P*The physical background of the different approaches can be seen in .4
the lungs more easily. The pioneering work on the interaction Figurenumber of molecules. This isotherm therefore continues to rise.
and had nothing to do with Teller assume that an adsorption site can bind an infinite
therefore tends toward a saturation value. Brunauer, Emmet, and
monolayer is possible, with all adsorption sites being equal. The isotherm
4.1|Adsorption In his theory, Langmuir assumes that only one .
From the BET isotherm, Junge derived his famousequation (34

assuming a BET (Brunauer-Emmet-Teller) isotherm according to that adsorbs on solid airborne particles with its saturation vapor pressure
Junge's original theory is based on adsorptionequation (32). ), which correlates the fraction Φ of a substanceP*, the particle surface θ
( cm² particle/cm³ air), the concentrationof the substance in the gas phase
KBET ∙p Cg /m³ air), and the concentration of the substance in the particle phase µ(
= [ ] (32)
mono (P∗ −p ) ∙ 1+ (KBET − 1) ∙p gCPA g/m³ on particles per air volume).µ(139
P∗
ηis the surface concentration of the adsorbed substance, ηmono CPA cJunge∙
= = (34)
is the surface concentration with a complete monolayer,p pressure, CPA +C g P∗ +c Junge∙
is the partialP* is the saturation vapor pressure, and KBET constant. For
is the BET adsorptionP* >>p and KBET according to Langmuir is obtained. The temperature dependence of theequations (32–34to
the adsorption isotherm ,1 >> ) is immediately apparent, since the vapor pressure is involved. According
equation(35), the parameter cJunge also depends on the temperature

η K∙Lp
= (33) via the desorption enthalpy ΔdH J/mol), the evaporation enthalpy(
ηmono 1+K L ∙p
| 60of 11
2TA B L E compartments are described

Compartments References
and partitioning coefficients for organic
compounds between different indoor Gas phase and airborne particles Weschler et al. (2008)124
of publications in which equilibria Liu et al. (2013)130
Compilation Salthammer and Schripp (2015)79
Wei et al. (2016)131,132
Gas phase and house dust Weschler and Nazaroff (2010)72
Surface and air Wu et al. (2017)133
Growth of organic films Weschler and Nazaroff (2017)73
Building products Bennett and Furtaw (2004)59

Shin et al. (2014)60
Eichler et al. (2021)134
Dermal uptake Weschler and Nazaroff (2012)75

Weschler and Nazaroff (2014)127
Gong et al. (2016)135
Gas phase and clothing Morrison et al. (2015)126

Saini et al. (2017)136
Licina et al. (2019)137
information, reference is made to the literature cited and in particular to the work by Wei et al.
For further129
4F I G U R E and Brunauer-Emmet-Teller
on a solid surface according to Langmuir
Adsorption of chemical substances
multilayer (BET)
monolayer (Langmuir)
sorbing surface
ΔvapH the (subcooled) liquid, and the moles of adsorption sites ( [TSPthe concentration of the chemical associated with particles (ng/
J/mol) ofNads (mol/cm²) on the aerosol.125 g particles) and µ] isCg =A g. The gas/particle partition coefficientK PA
is defined according toequation (37).
ΔdHvap−ΔH
nge Ju=10 6 ∙R ∙ T∙N ads ∙e (35)

R∙T
Csp
(37)
PA=C g
The study by Yamasaki et al.140air, which led to the derivation of
on PAHs in ambientequation (36dependence of gas/particle adsorption. Therefore, one finally obtainsequation (38fraction Φ.
), provided clear experimental evidence of the temperature ) for the particlebound
([ ])
F∕ PTS my + b Csp ∙][TSP KPA ∙SP] T[
og = y (36) = = (38)
Ag T Cg + Csp ∙TSP][ 1+K PA ∙TSP][
The symbolsAg and F refer to the sampling method. F matter in air ( The temperature dependence ofKPA is given byequation(39).36,141
/m³), [TSP] is themass of total suspended particulate
g/m³), µis the filter associatedmaterial (ngAg the gas phase (ng/m³), and N
ads ∙A TSP ∙T
ΔdHvap−ΔH
PA= ∙e R∙T (39)

refers to an adsorbent to collectmy and by are constants. Note that Csp =F / 16∙ P∗ L
|
Thus, the general form ofequation (39) is equation (40). 1.0

TSP = µg/m³10
ogKPA =m r ∙log P∗ + br (40) TSP = µg/m³50
L
DEHA particle bound fraction Φ

0.8 TSP = µg/m³100
Compound specific data formr and br found in numerous publications.
can be7,125,132
0.6
0.4
4.2|Absorption
0.2
partitioning tends to be more appropriate than an adsorptive model.
particles, Pankow proposed that an absorptive model of coefficient
of organic matter in indoor be used as a predictor for 142airborne 0.0
In this case, the octanol/air distributionKOA Given the large fraction 285 290 295 300 305 310
canKPA (see 41equation ).70 Temperature (K)
5F I G U R E bound fraction of DEHA in dependence of Particle-

1 oct MWoct
PA= ∙ 10−9 ∙K OA ∙f om_part∙ ∙ (41) concentration of TSP. was calculated fromKp_wiom m³/ 0.0283( 298 K) =
oct om MWom
g and ΔµwiomH kJ/mol. = 114.392K p_wiom temperature and
equation(45), and Φ was calculated from equation (38)
weight of -1With the density of ρoct and the assumptions that MW
kg/m³ 820 =oct/MWom octanol and organic matter) and γ-1octanol
molecular( 1 ≈oct/γom octanol and organic matter) -1coefficients of where ΔwiomH for the distribution between air and WIOM. Arp et al.
activity( 1 ≈equation (23) is obtained, which can be simplified to is the enthalpy147showed that Δ wiomH octanol Δ-1between air and
equation(42) with fom_part = 0.2.125 can be approximated by the enthalpy of distributionOAH Δ
from the pp-LFER approach according to vapH- air partitioning,
ogKPA = logKOA −12.61 (42)
Δ . For octanolOAH or by the (negative) enthalpy of vaporization
values can be calculatedequation (44).40
equation canbeused tocalculate the temperature dependence of
wiomH ≈ ΔOAHkJ(∕ 1.6mol) = + ∙V i − 9.7 ∙L i + 6.0 ∙S i − 53.7 ∙A i − 9.2 ∙B i −6.7
Thevan'tHoffKOA or KPAnaphthalenes, PCBs, dioxins/furans, PBDEs,
approaches. Corresponding data are for example available for polychlorinated (44)
temperature dependency can be determined from empirical
phase transition must be known for the respective substance. Alternatively, the For a narrow temperature range, the relationship betweenK p
To do this, however, the free enthalpy of the .131 _wiomvalues at temperatures T1and T2is given by equation (45).
phthalates,143organophosphate esters, 144and PBDEs. 145 ( )
ΔwiomH 1 1
nKp_wiom(T2ln=)Kp_wiom(T1) − ∙ − (45)
R T1 T2
4.3|LFER
between air and WIOM can be found in Salthammer and Goss.
/ particle distribution coefficient with a LFER approach according to (DEHA) at different particle concentrations [TSP].92 5Figure
It is also possible to determine the temperature-dependent gas For various SVOCs, enthalpies for the distribution ethyl hexyl adipate
Goss equation(27raises the problem that one needs the descriptors -2dependence of the particle-bound fraction for the substance di-
various types of outdoors,a ,b ,l ,v , and c aerosols. Salthammer and shows the temperature
). However, this aerosol. Experimental data are available for distribution between air and WIOM. The differences are shown in
for indoor aerosols. 92that the descriptors determined by Arp et al. on the concentration of total suspended particles, the
have shown146,147for the respective used to a good approximation distribution coefficient in WIOM, and the enthalpy for the depends
can also be - bound fraction of a non-ionizable organic compound essentially µ
- matter (WIOM) is given by the partitioning coefficient The particle 6Figure for a constant concentration of [TSP] =25
The absorptive partitioning between air and water-insolubleorganicK phthalate). The calculation is based on the pp-LFER approach
p_wiomThe temperature dependence of .Kp_wiom by the van't Hoff phthalate), BBzP (butylbenzyl phthalate), and DEP (diethyl
can be describedequation (43), g/m³ for DEHP (2-diethylhexyl
with a high Δ K; 51% at wiomH hexadecane/airpartitioncoefficient − =
ΔWIOMH 1 kJ/mol and a high logarithmic 116.7L K). BBzP with Δ = 308DEHP
nKp_wiom = − ∙+ onstc (43)
R T 288is largely bound to particles (96% at 12.70wiomH kJ/− =106.2
| 60of 13
1 25and 4µPlanck's law is in the infrared range between 9at

m.µm with a maximum
µg/m³) 25Particle bound fraction Φ (TSP =
DEHP(Δ w 116.7iomH =- kJ/mol)
0.1
( ) Tair +T r forairvelocities (<m 0.2∕s)
op=A op ∙T air + 1 −A op ∙T r ≈
2
(46)
0.01
BBzP(Δ w 106.2iomH =- kJ/mol)
0.001 with Aop =h c/(hc +h rad) is a function of the convective (hcradiative (

) andhrad,7726) heat-transfer coefficient. In ISO 150A op velocity
values are tabulated in dependency of the airAop m/s. This allows
4E-1
DEP(Δ 82.1wiomH =- kJ/mol) for air velocities <0.2 0.5 =Top calculated from the mean of
The higher specificTair and TrFanger .2heat capacity of the water of
5E-1 to be approximately thermal sensitivity under normal living conditions

285 290 295 300 305 310 that the humidity has only a minor influence on the Section (cp
Temperature (°C) Δ2K) compared to that of dry airwith ∙kJ/(kg4.2O) = cp stated
at high air humidity and temperatures (see the specific enthalpy
6F I G U R E 25DEP in dependence of temperature for [TSP] =
K) becomes noticeable only∙kJ/ (kg 1.0air) = 5.2(H with heavy activity, or
g/m³. µParticle-bound fraction of DEHP, BBzP, andKp_wiom
energy content of dry and humid air can be compared using
and ΔwiomH were taken from Salthammer and Goss.92K p_wiom
was calculated fromequation (45) and Φ was calculated from increase in skin temperature and core temperature, whereupon
equation(38). the body reacts immediately with cooling mechanisms. The an
to fraction of water vapor in the air. Also, some water may condense
mol andL K. For DEP with Δ = 308at 1%K and 288at 13%between on the skin; this process is exothermic. Combined, these lead
and Goss.9.95 Φ wiomH kJ/mol and − = 82.1L is always <10 =6.75 Φ −4 into the sauna air. Heat transfers more rapidly with a higher
varies under consideration. All data were taken from Salthammer when, during sauna infusions, steam is rapidly introduced
in the temperature range92 suggest the sensation of a sudden increase in temperature /kg at
). It is the different heat capacities of air and water that forairHexample
0kg of dry air and is by definition 1pressure, this is related to
5|THERMAL ENVI RONMENT . At standardT K. = 273.15 7Figure kJ the method specified by Schmidt.
THE HUMAN humidity. The calculation was carried out using ASHRAE Standard
shows enthalpies for different temperatures151 .55and relative

5.1|Human perception of temperature to when exchanging indoor and outdoor air. McArdle et al.
shaded air. 4area shows the approximate human comfort range according
predicted percentage of dissatisfied (PPD). The PPD value quantifies Enthalpies can, for example, be used to calculate heat balances152The
percentage of people in a large group of occupants exposed immersed in 28body cools down faster than if you are surrounded by
to the same thermal conditions who feels too warm or too cold. the °Cwarm water, the28°C warm using a simple example: If you are
the thermal sensation is the PMV (predicted mean vote) designed explain the influence of heat capacities
by Fanger, which can be put into a functional context with the of th century.19has been known since Pettenkofer's work in the mid-
radiation in the surroundings are perceived as optimal. A measure The importance of adequate air exchange in residential buildings1
well heat exchange is significantly influenced by factors such as ambient However, as pointed out by Nazaroff,153body caused by air movement.
heat air temperature, clothing and sweating and shivering. Thermal “draft”). This term describes an unwanted local cooling of the human
- being arises when the air temperature, humidity, air flow, and uncomfortable and experience a sensation known as "draught" (or
are dependent on constant heat exchange with their surroundings to higher air velocities and turbulence. People perceive high air velocities
through convection, radiation, evaporation, and conduction. This steadily with the air exchange rate. A higher air exchange usually leads
As warm-blooded beings, humans148,149 ventilation air. Moreover, it is not the case that thermal comfort increases
The operative (also called perceived) temperatureTop ,7726to ISO by concern about the energy costs for the thermal conditioning of the
occupant would exchange the same amount of heat by radiation plus high ventilation rates are tempered154
convection as in the existing non-uniform environment. According on the temperature. At 155°C. 26was significantly higher than at
is defined as the uniform temperature of an enclosure in which an150 also depending an air velocity of 20Fanger and Christensen
to Top can be calculated from the air temperature Tair temperature dissatisfied people of draught resulting in discomfort, the percentage
surface temperature of Tr according to equation (46).T r according of the subjects had a feeling 15%m/s, more than 0.2°C, the number of
as black bodies. For a body with a 301and the mean radiant clothed with increasing air speed due to the perception of draught. From
K (28°C), the majority of radiation in the room, which are interpreted that the satisfaction with the air quality decreases significantly
is the mean value of the heat radiation of all surfaces people 100showed through studies on
|
140
( )
RH 80% 0.4I =∙ Tair+ Tw +8.3 (47)
RH 70%
120
Enthalpy of dry and humid air (kJ/kg)
RH 60% Tair dry-bulb temperature, which corresponds to the air temperature.
100 RH 50% is theTw is 100%by direct evaporative (adiabatic) cooling. At RH <
RH 40% - bulb temperature, which is the lowest temperature that can be achieved
80 is the wetTair >T wis 100%and at RH = ,Tair =T w
RH 30%
RH 20% determined directly using a psychrometric measurement. Alternatively,

60
RH 10% The wet-bulb temperature can be .Tw can be calculated from Tair
40 RH 0% andRH using a formula derived by Stull.168
index and discussed critically by Epstein and Moran. Giles et al.

20 Various relationships were derived for the167Equation (48discomfort
) by169links DI directly to Tair and RH.
0
0 10 20 30 40
I =Tair − 0.55 ∙ (1 − 0.01 ∙RH) ∙ (Tair − 14.5) (48)
Temperature (°C)
7F I G U R E Enthalpies of dry and humid air ΔairH according to to the different calculationmethods. According toEpsteinandMoran
Schmidt.151region considered “comfortable” is shown in the shaded box,
The interpretations of DI differ slightly due167or Giles et al., 169et al.
The4that the area is dependent on clothing, air speed, and adaptation
absorbs heat from air, which leads to hyperthermia. Giles
recognizing
this value, the body can no longer release heat to the environment, but
state of medical emergency. Above :32severe heat stress; and DI > :32 <
the well-being and performance of people who live and work indoors. increasing thermal discomfort; 29 < DI :29no heat stress; 21 < DI < :21 <
Thermal comfort has a major impact on156–159the perceived air quality. the following ranges can be defined. DI169Fahrenheit and Celsius scale.
to temperature and humidity, the carbon dioxide content also influences the Discomfort Index a total of six categories with reference to both the
year study in165Chineseresidences, itwasshownthat, inaddition-1 define in their work on
In an extensive160increasing carbon dioxide content in the breathing air. .7243WBGT (wet bulb globe temperature) index according to ISO
studies have shown that the cognitive abilities of people decrease with Another method to calculate the thermal stress is the170using
carbon dioxide is also a key parameter in assessing air quality. Several applies to the indoor environment, the WBGT is calculated
This again underlines that161–163occupancy rates such as school classes. In the absence of direct solar radiation, whichequation (49).
hygienic comfort range for carbon dioxide, especially in rooms with high
which, in addition to temperature and humidity, also take into account the 0.7BGT = ∙T w + 0.3 ∙T air (49)
well-being are omitted. Alternatives have therefore been suggested
means that other parameters that are also important for physiological In fact,equation (49) involves the globe temperature Tgalso Section
air temperature and the relative humidity (Mollier diagram). However, this temperature measured at the center of a hollow black metal sphere (see
example the air temperature and the surface temperature, or the This is the .6). For indoor spaces, it can be assumed that Tg ≈T air
comfort diagram usually only takes two parameters into account, for Finally, ISO7933 .171in terms of body core temperature and sweat rate.
The classic thermal164,165 to evaluate the response of active standard persons to thermal stress
tool for the predicted heat strain (PHS). This model has been developed
provides a sophisticated calculation
5.2|Thermal discomfort and stress

5.3| Heat exchange of the human body
climatic conditions, for example when the metabolic rate is high.
impairments that go beyond pure subjective perception. However, a a bicycle ergometer, the–20%mechanical work yield is approximately
physiological feeling of stress can also develop under moderate 25% at medium power. man-machine is not particularly efficient. On
can experience thermal stress. This means physiological From an energetic point of view, the152is significantly lower.
the thermal environment, they find the situation comfortable. Slight For other activities, the efficiency2were first performed.
deviations from thermal comfort are referred to as discomfort. For when extensive and accurate measurements of body temperatures is
certain combinations of temperature and relative humidity, people years ago 150°C lower than it was 0.4°C, a value that is about 36.7
When a person is satisfied with152 constant. Today, the core temperature of a healthy adult
load using temperature and humidity measurements, Thom A certain amount of energy is needed to keep the body temperature
In order to classify the thermal166scale. Epstein and Moran 172is done by radiation, convection, conduction, or evaporation.
proposed a discomfort index (DI) based on the Fahrenheit167Thom work done and heat dissipated to the environment for cooling, which
provide theequation (47) modified for the Celsius scale. This temperature is maintained by balancing metabolism with
| 60of 15
According to Parsons,148equation (50balance of the human body. For air velocities <3 m/s, convective heat-transfer coefficientsh c
) applies to the energetic K).∙W/(m² 15K) and ∙W/(m² 5are between ,174
The transfer of heat by conduction is proportional to the contact area
̇ −Ẇ =Q evap+ Q̇rad+Q conduct +Q̇ convect+Q S (50)
AskinK)) inversely proportional to the thickness ∙conductivity λ (W/(m
, the thermald conductor and proportional to the temperature difference
evapo- is
̇ the rate of mechanical iṡ the metabolic rate of the body, of the transferring heatTskin -T air which the heat exchange takes place.
wȯrk, andevap ,rad, conductand ,̇ convectare heat losses by of the two bodies, here skin and air, between
rȧtion, radiation, conduction, and convection, respectively. S is the

Askin ∙ ∙ (Tskin −T air)
parameter. For the body S= 0the body is in the heat balance; , ̇ (53)
conduct=
d
fȯr S> 0the body temperature will rise; and for ,̇ S< 0,hėat storage
temperature will fall.
h) (kilojoulesperm∙rate (BMR). The BMR is approximately140–170kJ/(m² of the body of the surrounding environment 54equation surface
of energy required to maintain vital functions is called the basal metabolic law ( energy is determined by the ratio of the temperature
The minimum amount2kJ of energy. 21body can generate approximately ), the transmission of radiantTskin According to the Stefan–Boltzmann
L of oxygen, the 1min) oxygen (per kg body weight and minute). With ∙/(kg to the mean radiant temperatureTr.A skin effective surface, and
mL 3.5physical exertion, a person consumes approximately ε can thereforeσ = 5.67·10−8W/(m² K 4.0.95be assumed to be
h) for adult women. Without∙150 kJ/(m²–130adult men and is the radiative properties of a black body. The emission coefficient
bodysurfaceandhour) for152RMR (in kJ/min) can be obtained from ) is the Stefan–Boltzmann constant. Skin has almost the
kJ/(kg/min). The 0.074This results in a resting metabolic rate (RMR) of
4
̇ =A skin ∙
rad ∙ ∙ (Tskin 4−T r ) (54)
equation(51), where mbody is the body mass in kg.
21∙ 3.5 ∙mbody

MR = (51) When the temperature difference is small,equation (54
1000
) can be approximated by the linear relationship (55).
( )
̇ (55)
rad=A skin ∙h rad ∙T skin −T r
corresponds to a medium to heavy load. consumes 6.1of
mL of oxygen per minute has an energy expenditure 1500MET, which
is metabolic 70equivalent (MET). For example, a person weighing De Dear et al.174the linearized radiative heat-transfer coefficient
kg who be expressed in multiples of the RMR, the name for this and also provide measured data from previous publications.h rad
The level of physical exercise can now discuss an equation proposed by ASHRAE for calculating shown)
conditions. 58MET = 1relates to power and body surface area with ( not
Another definition of the metabolic equivalent2W/m resting environment. The20kJ/mol at 44.2enthalpy of vaporization of water is
°C (see is used by the organism to release heat to the
typical body surface 104m², so that a thermal output of 1.8area is
body. The associated thermodynamic process on the skin surface
W results under standard person in thermal equilibrium. The Evaporation describes the transepidermal3Table water loss of the
1the skin depends on the ratio of the partial water vapor pressures of
metabolic rate of a sitting ),̇ the convective heat-transfer .173
that 30 L of water. The amount of heat that can be given off through
coefficient equation (52This corresponds to the resting convect kJ of heat is required for the evaporation 2430°C. This means
kJ/mol at 43.8) and H2O,skin and the surrounding air H2O,air (see 56
depends on the body surfaceAskinAccording to convective heattransfer
equation).A skin is the exposed skin surface, and α
difference between the skin and the ambient air and on the evapis the evaporative
the temperature ,hc.
̇ (52) heat-transfer coefficient.

convect=A skin ∙h c ∙ (Tskin −T air)
3TA B L E λ, specific heat capacities c

λ cp ΔvapH ΔH
Heat conduction coefficientspΔ
W/(m·K) kJ/(kg·K) kJ/mol kJ/kg
at different conditions ,vapHenthalpy Δ
and ,Henthalpy of evaporation and water Water (liquid) 20°C)( 0.598 20°C)( 4.18 20°C)( 44.2 20°C)( 84.1
( energy content) of air Water (gas) 100°C)( 0.024 100°C)( 1.86 100°C)( 2676
Air (dry)175 20°C)( 0.025 20°C)( 1.01 20°C)( 20.1
Air (50% RH)175 20°C)( 0.025 20°C)( 1.03 20°C)( 38.6
Air (100% RH)175 37°C)( 0.026 37°C)( 1.06 37°C)( 142.8
Epidermis176 0.21–0.26 for skin)( 3.4177
Dermis176 0.37–0.52
Note:RH, 0%The enthalpy is related to T K and = 273.15pair Pa (Δ 101325 =H kJ/kg). =0

|
body. The drier the ambient air, the easier it is for the water to evaporate.
̇ (56)
evap=A skin∙ evap∙ (pH 2O,skin − pH2air O ,)
skin evaporates. The heat required for evaporation is withdrawn from the
the body's heat balance if the water on the
The skin surface area can be calculated using the Duboisformula (57
.100%for cooling as long as the relative humidity is less than ), wherehbody is the height in cm and mbody is the body weight in kg.
core body temperature, evaporation is the only possible mechanism

% humidity, as long as the temperature of the skin surface is higher
() 25 ∙h 0.725
than that of the environment. At ambient temperatures above the Askin m 2= 0.007184 ∙m 0.4body body
(57)
loss. 100vapor can still be released into the environment even at
again decrease in their effectiveness to facilitate body heat as well as the fraction of the total surface area that is clothed,
Since thewater vapor pressure is temperature-dependent, water be made between clothed and unclothed skin by Gagge et al.,
also increases significantly, while conduction and convection In reality, when calculating the skin surface area, afcldistinction must
work, where the core temperature increases by up to insulation. The heat exchange depends on the properties of
°C depending2on the workload, the heat dissipation through evaporation clothing (heat-transfer coefficient, water vapor permeability) and thermal
and then increases steeply at higher temperatures. During physical the amount of coverage. A measure of the thermal output of clothing the
30almost constant up to an ambient temperature of around that reduces the loss of body heat is the "Clo" unit introduced
°C these three mechanisms. The proportion of evaporation remains In most cases, people need clothing for .178 ,9920to EN ISO
temperature, the body absorbs heat through small at temperatures above defined to characterize the thermal insulation of clothing. According
proportion of conduction, radiation, and convection35exceeds the body used in practice. Various parameters are currently air movement of
thermoregulation steadily decreases and becomes negligibly temperature, the unit is considered out of date, but at a temperature of 0.1is still widely
°C. If the ambient temperature in and an ,50%°C, a relative humidity of less than 21m/s. The Clo
heat conduction and convection dominate. With increasing ambient to clothing for a sitting, resting person who is in thermal equilibrium
no wind, the individual heat transport mechanisms contribute 10% K/W. This corresponds∙m² 0.155coefficient. By definition, 1 Clo =
heat dissipation of humans in the following proportions: 45% % and reciprocal of the heat-transfer surfaces), the total insulation (179
radiation, 25% conduction and convection, 20% evaporation, and to the insulation basic (intrinsic) insulation (I which is proportional to the
respiration. Under these conditions, heat radiation as well as resistance to dry heat loss between twoIT these include the thermal
50°C, a relative humidity of21At an ambient temperature of 152 surface), and the air insulation clothing or the skin surface). EN ISO Icl
of respiratory air. From the enthalpies in minute a person inhales surface to the environment), the the skin surface to the outer clothing
L of ambient air per minute and exhales 7.5the same amount reference to the Clo value.Ia (9920thermal insulation from the body
per are shown in 15L, at 0.5respiration. At rest, the tidal volume is surface air layer around the outer of other parameters, and the respective
In comparison, there is little heat loss through 3Table breaths 179(thermal insulation from thermal insulation of the boundary
that the maximum heat dissipation under these conditions–10is regulates their units, derivation
15 W. The various processes of human energy expenditure calculated Since temperature and air humidity significantly influence the human
and taking into account the respective air density, it can be 8Figure heat exchange with the environment, these parameters also have
It should be made clear that sweating only contributes to . a significant influence on the acceptance of surrounding air. In
Metabolic heat
Food
production
Heat loss
Radiation
Heat gain
Radiation Convection
Convection Conduction
Conduction Evaporation
Respiration
Mechanical work 8F I G U R E in the thermal environment

Heat balance of a person
| 60of 17
experiments with human subjects in clean air, Fang et al.180enthalpy.

acceptance of air quality decreases significantly with increasing air °C20 °C35
found that the
5.4|Human body and surface temperatures
distribution35°C and 20in the human body as a cross-section at

°C is shown in heat exchange with the environment. The temperature
can be varied. The body uses this capability to regulate the of
have a uniform temperature distribution. Only the essential37
(brain, heart, liver, kidneys, and lungs) are constantly does not
via the bloodstream and kept at a core temperature central organs
°C. In contrast, the supply to the peripheral vasculature supplied
The human body 9Figure.
50%°C and 21of heat transfer to the environment at 70%about
As already described, convection and conduction contribute to with a RH
areaaveraged surface temperature ( to the operative temperature, 104
are equal (and are therefore equal 70Therefore, a .TsurfaceW metabolism, the
kg individual and mean radiative temperatures
conduction). Assuming that the indoor air temperature

9F I G U R E Temperature profiles of the human body at different
enough to transfer about have high emissivities, we can combine 73
ambient temperatures according to Aschoff et al181
and radiation (neglecting the surface of their clothing) must be high
to the environment as shown in TopW to the environment by convection
loss) from an occupant surfaceequations (52) of the occupant (mostly humidity, clothing, and other factors on skin temperature.
) and that all surfaces transfer (also known as sensible heat temperature, relative182
) and (55) for dry heatequation (58). range of temperatures across the body at different environmental
( )( ) conditions. In an early review of skin temperatures, Beirman
̇ ∙ Tsurface −T op (58)
rad+Q convect =A surface ∙h rad +h c
of skin temperature measurements associated with metabolism
and comfort studies; here, we highlight a few that capture the
de Dear et al. 4.5- transfer coefficient is typically reported to be about vary across the body. There exists a substantial literature
The human radiative heat2K).∙174W/(m reported by in a fairly narrow range, temperatures same ambient temperature range.
example, we will use the whole-body forced convection expression of forehead, trunk, and thigh) were closer at 183skin temperature lie typically
temperature, 174to estimate hc W/(m = 5.02m/s. For 0.3K) at an air speed of∙ °C for that33.5°C and 32While the average surface and
Asurface m 1.8 =2and an ambient temperature Top For this °C, respectively, while proximal temperatures (an average22°C and
within the range typically considered25 =Tsurface“comfortable.” 16°C at ambient temperatures of33.0°C and 27.5averaged
°C, then the area-averaged surface clothed person. This value lies a metabolism study male hand and foot skin temperatures
°C for a fully34body, the skin temperature is approximately conditions, the extremities are cooler than the trunk. For example, in
2 that of an unclothed/1heat-transfer coefficients from skin to air are environments more typical of indoor feet ranging from as low as 45
balancing heat flux across clothing and assuming the combined °C in a cold environment to as high as15°Cwhen exposed to heat. In
is an area-averaged value of the surface of clothing (and reported measured temperatures of hands and
some skin) exposed to air. Under clothing, skin is warmer. By person, this responsive to environmental conditions and can be much between
°C. For a clothed29is , or much warmer than the trunk skin temperature; Bierman to be more
health has excellent nomographs showing the modeled influence of °C, but the temperature of extremities tends36.7°C and 33.6cooler
ASHRAE Handbook - Fundamentals chapter on physiology, comfort, and temperatures varied temperature ranged from 184°C. 32.5°C to 27foot
36°C. The–33- averaged skin temperatures tends remain between about °C, and34.5°C to 29.5°C, hand 35.5°C to 33reported that trunk
not subjected to extreme climatic conditions, the true range of area °C, the trunk skin29°C to 21temperatures ranging from
when cold), and altering behavior (donning or removing clothing). When In a set of comfort studies that exposed subjects to environmental185
temperature to control dry heat loss), altering metabolism (e.g., shivering conditions. We186combined those to generalize the results as shown in
the flow of blood to capillaries near the skin (changes skin Olesen across body sites for many temperature and clothing
the core body temperature by controlling evaporation (sweating), altering published and unpublished experiments and reported results
many important details; most important is that the body regulates collected skin temperature data from multiple 10Figure
This simple analysis excludes for coolest skin temperatures, mean and warmest skin temperatures
|
0 1F I G U R E according to Olesen
Low Mean High maximum (high) human skin temperatures
Minimum (low), mean and186
visually the temperature variability across the clothed11Figure body. for metrological institutions and the international system of units.
measured. Also shown is a thermograph image ( demonstrates - precision primary thermography is essentially of importance
) of the authors that used to measure the temperature. Other primary methods are based
. and/or when the room temperature is cooler (i.e., thicker for a larger on acoustic effects or on frequency measurements. In practice, high
temperature difference between the body and surrounding air) measurement. Alternatively, the relationship between the pressure
layer is generally thicker when nude of air varies in thickness from and the dielectric constant of a gas, for example helium, can be
cm depending on conditions 15to 1and location on the body. The constants. The principle of the gas thermometer assumes that gases
to room temperature across a thermal boundary layer. This layer at low pressure and not too high temperature obey the equation
the body increasing the rate of transport of contaminant of state for ideal gases. If the volume is constant and the density
(and thermal energy) between air and the surface. The around is known, the temperature is obtained directly from the pressure
temperature around the body drops from skin temperature mass and temperature-independent17
surfaces and the surrounding air induces natural convection temperature. That voltage is non-linearly dependent on the
The temperature difference between occupant187 temperature difference between the connection and free ends. different
can be much lower than for other indoor surfaces (see Section effect. When connecting two wires of different materials, a voltage
tends to be ~5–15°C higher than ambient, some chemical reactions can be measured at the free ends if the connection point is at a
can be faster while equilibrium partitioning to the skin surface used in field measurements and are based on the thermoelectric
and ambient temperatures, and a several cm-thick boundary layer interpolation between these fixed points is carried out via platinum
27 of warm air surrounds the body. Given that the skin temperature resistance thermometry. This method is convenient to calibrate
°C–36°C. The surface temperature of clothing will lie between skin thermometers for everyday use. Thermocouples have also been
indoor environments, the skin temperature ranges between about melting, solidification international temperature scale from
Overall, we see that in most8). of pure substances. The fixed points are used, which refer to
thermometric ,)90ITS-( 1990or triple point temperatures
in thermistors. For calibration according to the currently valid

6|TEMPER ATURE MEASUREMENT or alcohol. Today, most field thermometers take advantage
of the temperature dependence of the electrical resistance mercury
that changes with temperature can be used for measurement. the based on the thermal expansion of liquid substances, for example
additive. On the contrary, a universal temperature scale follows from2 The classic thermometers are
nd law of thermodynamics. In principle, any physical quantity carried out with a globe thermometer, which measures the globe
temperature, in contrast to a unit of mass or length, is not to the temperature. With typical resistance 0.5is usually better than
As an intensive thermodynamic state variable, the the air temperature, the accuracy be performed with regard
system that links temperature with other independent quantities K. Thermal comfort measurements are thermometers for measuring
Primary thermography is based on a well-understood physical In the indoor environment, there are various measurement tasks to
| 60of 19
7 | TEMPER ATURE IN BUI LDINGS
they were particularly informative. that are reasonably recent (since

but also included some that ,)2000were smaller or earlier because
and estimated based 10include field studies with greater than
field measurements, we on measurements, thermostat settings, models
buildings/locations and on a simplified thermodynamic analysis. For
the goal of establishing the typical values and reasonable ranges of
values, the following is a brief review of indoor temperatures based
With
7.1|Residential measured indoor air temperature
sometimes far too many to include in this review. Most of those reported here
course, and provide were focused primarily on measuring temperature and
of regional indoor temperatures. humidity. These are non-comprehensive, of
several high-quality snapshots
primarily in the northern hemisphere where most measurements

are have been performed. There have been many studies that include
temperature as one of the many measurements, and there
of residential measurements in several regions of the world and
Here, we report results
11F I G U R E °C (picture by Jørn Toftum, DTU)24.1temperature of Europe |7.1.1

Infrared thermograph of the clothed authors at a room air
ranged from 192°C. 15°C to 12.3mean temperatures ranging from

temperatureTgabsorption of radiation. The mean radiant temperature temperature range of 21.5°C to 13Beizaee et al. mean temperatures
positioned inside a black hollow sphere made of metal that heats up upon one of the warmer homes ranged from 19°C to 15°C for external daily
The sensor is .Tr can then be calculated from Tg velocity close to the globe. °C for an external28.5°C to 21°C. In a cooler home, indoor daily
depends on the globe diameter, the emissivity of the globe, and the air homes were slightly cooler than newer homes. The temperature in
and also188properties of black bodies and may have a lower emissivity. summertime overheating, they did not report minimum1.7were
must be taken into account that real surfaces deviate from the radiation homes were cooler than semi-detached, terrace potential for
temperature of a material. Under certain circumstances, however, it or flats (apartments). Average maximum temperatures values. Detached
is now the common non-contact method for measuring the surface °C warmer in flats than detached homes. Older homes
probe and the surface can be established. Infrared thermography external average temperature was 30.3reached temperatures up to
the accuracy depends on how well the contact between the measuring temperatures were within a similar range. Some individual homes °C; the
methods are mostly used today for long-term investigations, whereby of25.8°C. Bedroom mean to 15.3°C. Since their focus was on the
To measure the surface temperature, contacting189wet-bulb temperature 21.8°C in living rooms with an average mean temperature
TheTw 7726measuring principle and the environmental conditions. ISO in 18.9in England. They observed mean values that ranged from
parameter is measured, there are basic requirements regarding the 2007residences during the summer of 193°C of indoor temperatures
the temperature difference between the two thermometers. Whatever conducted a survey
leads to a higher heat loss. The relative humidity can be determined from and Kane in living rooms ranged from 193observed by Beizaee et al.
drier the air, the faster the adiabatic evaporation of water, which then °C, very similar to the range25.2°C to 19Also in England, Lomas
of which is wrapped in cotton cloth moistened with water. The in Leicester. They observed that the mean daily indoor temperature
is measured with a psychrometer. This consists of two thermometers, one homes 230measured summertime temperatures in 192
150techniques have been published by Camuffo and Fernicola homes were heated in the Beizaee et al. 193room during summer; 14 of
operative temperature. Reviews of indoor temperature measurement homes heated at least one 230Somewhat surprisingly, 30 of the 192
temperature, absolute humidity, air velocity, surface temperature, and °C. Interestingly,14.8°C and lowest 32.6hourly average temperature was
characteristics for measuring air temperature, mean and plane radiant °C, highest22.2°C. In unheated homes, the mean was 37.4room reached
specifies minimum190as well as Camuffo. 191 °C and the hottest23.5rooms during summer, the mean temperature was
study. In homes that actively heated

|
between the living room and2°C to 2bedroom ranged from − heating periods. In general, renovations resulted in increased
°C with a median value near zero. that the mean temperature difference average indoor temperatures. For example, Földváry et al. during
they reported on average indoor temperatures apartments). Oreszczyn et al.
Yohanis and Mondal from 194widely even over short time periods. Several European studies evaluated199the effect of energy renovations
°C, closely followed outdoor temperatures and varied21to 10 deviation among energy renovation increased by greater than
third group did not heat their homes and temperatures, varying of °C and the distribution1of temperatures was flatter (lower standard
of mean daily temperatures ranging from approximately –22 2.6apartments in Slovakia after were 20that the mean temperatures in
second group maintained a higher and more stable temperature observed200°C warmer. In a related study, Hong et al.
22°C. A–1823°C; this group was considered more energy wasteful. The °C warmer than pre-intervention homes; bedrooms1.6
to provide a reasonable level of comfort with a modest variation temperature criteria. Therefore, the reported data are not sufficiently
energy multiple rooms in each house. They grouped homes by comprehensive for this review. However, they showed that the living
studied 3mean yearly temperatures. One group prudently used rooms of retrofitted homes (heating upgrades and insulation) were
homes in Northern Ireland over one year, instrumenting 25different of data that did not meet the outdoor 30%excluded
homes under identical outdoor air temperature conditions (5°C), they
°C, respectively.17.6°C and 14.6low and high temperatures of energy conservation retrofits. Because their goal was to compare
characteristics. 15.8in winter, mean daily indoor temperature was urban areas of England. The homes were undergoing in approximately
variable. The former is thought to 141In a survey of 195°C, with mean 20022002 and–2001homes during winters of 1000– 2003 in five
of heating and better building thermal and steadier vs. cooler and more temperatures in retrofitted homes by 201the contrary, Langer et al.
residences in Northern Portugal be associated with more use mean temperatures2.8°C, 1.9°C, and 1.2recorded wintertime
authors observed two profiles of dynamic temperatures: warmer by °C, respectively. On combination of insulation and heating increased
and 10 °C than bedrooms. The1.77°C. Living rooms were warmer by –5 showed that insulation, heating, and the202Swedish housing stock.
and 24%th percentile mean daily temperatures were separated in 90th 20 was not statistically different from measurements taken from the
°C. The14of bedrooms were below 35%of living rooms newly constructed conventional homes in Sweden 20passive and
by WHO (21°C in living rooms). The mean daily temperatures found that the mean indoor temperature in203
were well below the comfort temperature recommended
The authors noted that temperatures
19.9in France were studied for indoor environmental and air quality. was Asia and Australia |7.1.2
cities 74Over two years, 567 dwellings from 196°C). 1.3°C (SD
multifamily apartments was 2.3°C (SD 21.1apartments was Singh et al.204°C. 29.4average across houses recorded in Tezpur at
°C), retrofitted multifamily1.8°C (SD 20.4°C), and single-family houses °C in Imphal, and highest in July with the highest13.7in January, as low as
energy-efficient dwellings found that the mean temperature in new days from each season). Mean indoor temperatures were lowest
72houses during the heating season. Also in France, a survey of homes in North-eastern India during January, April, July, and October (25
than in single-family humidity was 1that apartments were about vernacular 150studied
minimum and maximum of 9.1with a standard deviation of 48%°C warmer residences in Beijing, which lies above the H-Q line, Sun et al.
°C, respectively. Relative temperature was 29.3°C and 12.5°C. They observed 1000- Q line, than cities just above. For example, in measurements of
°C and a2.4°C with a standard deviation (SD) of 20.8 in winter will generally be cooler in cities just below the H as a
included in the study during all seasons. The mean daily indoor heating only above the “H-Q” divide, defined Shanghai, Shi et al. 0
homes were not evaluated for the full period, but homes in January. Therefore, indoor temperatures policy allows space
week; therefore, individual 1home was evaluated as a snapshot for In China, a regional climate and space heating205°C isotherm
Each197 °C. Below theH-Q line in20.5temperature (December–February) of
year. 1apartments in Finland were instrumented each for 94and temperatures: Baotou, outdoor 206°C. 11.4reported a mean temperatures of
intended to evaluate indoor environmental quality in pre-renovation Yan et al.207found a mean winter in outdoor mean
apartments in north-eastern Europe, 96 apartments in Lithuania above the H-Q line during the heating season. The of residences
and also noted198a higher frequency of window opening in Lithuania. cities were chosen to represent significant differences cities in China
In a study in Finland preferred warmer indoor temperatures measured temperatures in apartments in threeTmean three
temperatures were lower than in Finland at ,)2.2°C (SD 17.9 °C, number11− =n Yinchuan, outdoor = ;63Tmean °C, 5.6− =n =
)1.6°C (SD 19.6respectively. The authors suggest that occupants values ranged from ;69Tmean °C, 5.8 =n for all residences. = 87.2to 6.1
°C). In Lithuania, both1.6°C (SD 20.5and or window) temperature was Jiaozou, outdoor one another, 15–24°C. Indoor relative humidity
by thermographic camera. In Finland, median1.1°C (SD 22.7was th percentile were similar to90th to 10Baotau and Jiaozou, the
in the center of a living room) temperature location as identified Yinchuan, the9th percentile temperatures were 90th to 10
°C) and cold spot (often near a balcony door warm area (typically °C–21°C; for indoor temperatures covered a broad range. In
sensors were deployed: one in a cold location and one in a warm °C for Baotou, Yinchuan, and Jiaozou, respectively. Notably, the17.2
Two temperature/humidity °C, 20.9°C, and20.6Indoor mean temperatures were .44
| 60of 21
Han et al.208 .62%°C and relative humidity of 28.7temperature of < 1°C temperature difference between living room and bedroom.
north, Sun et al. observed a summertime mean °C. Unlike several other surveys, they observed24.6°C and 11.2from
summers, respectively. Further 2004and 2003for 78.4%and 71.3%were ranged indoor temperatures (standard deviation) of 2.7°C (SD 17.7
°C for the two summers combined. Mean indoor relative humidities36.4of from 2.6°C (SD 18.3°C); average minimum and maximum values
°C and maximum17.2the two summers, respectively, with a minimum of and (combined) Washington and Oregon homes had average ranged
°C for30.5°C and 29reported mean indoor temperatures of °C. During the heating season, the New31°C and 20.8°C) and York
Of these, 45% had air conditioning. They .2004and 2003the summers of Florida and New York; average minimum and maximum values
Chinese cities (located in hot and humid region, below H-Q line) during the cooling season, the1.7°C (SD 23.3°C) and 1.8°C (SD 25.8of
residences in three 26studied indoor temperatures home to compare spatial differences. During
homes in Brisbane, Australia, Asumadi-Sakyi et al. 77In a study of 209 °C), respectively, from New York and Florida living rooms had average
year, theaverageminimumindoortemperaturewas13°Candmaximum34°C. multiple rooms in each
°C, respectively. Over the whole27°C and 19season mean temperatures of Booten et al.217set of homes; these we discuss in the next section.
observed cool-season and warm also collected thermostat set points from a much larger
season, respectively. They were approximately 31°C and 13.9and
values cooling seasons was 27.2°C and 10.6°C during the cooling
Africa |7.1.3 season °C), respectively. Based on figures, minimum and maximum
0.8°C (95% CI =23.7°C) and 0.6°C (95% CI = 19.6°C during the heating
In Johannesburg, South Africa, Naicker et al.210months of the year. home; instead, they are an aggregate of spot measurements 327of
did not extend into the warmest or coolest mean was about homes. The mean temperature during the heating and each
toMay of 26°C and warm season about 19the measurements a site; then, sensors were moved to a new site. Therefore, they
Cool season indoor temperature .2014°C, although from February do not reflect comprehensive measurements over a year for at
low-cost homes 100measured indoor temperatures in report, these temperature from a non-representative set of
Bouden and Ghrab211°C. 9.2a standard deviation equal to one or more days all major climate zones. Based on our reading of the
– 39.2°C)andalsoexhibitedthelargestspread in indoor air temperatureswith US homes across 327were hourly measurements taken over
in the city of Kef experienced the most extremetemperatures (4.8°C collected measurements of indoor
°C. Measured indoor air temperatures from buildings39.2°C to 28.5from conditions. They218found that only the indoor absolute humidity (
°C; maximum values ranged15.7°C to 4.8values ranged from Nguyen et al. well outdoor conditions would correlate with indoor
°C for the six cities. Minimum23.5°C to 20.5the whole year, ranged from respectively. Their goal was to determine how ,55.5%and ,23.3% ,%
climatic zones) in Tunisia over one year. Air temperatures, averaged over and 47.5°C and relative humidity values of23.4°C, 19.2°C, and 19.8of
offices in six cities (2 36houses and 61measured indoor temperatures in temperatures 75%Boston, MA USA. They observed median, 25%
Nematchoua et al.212as comfortable. Komolafe and Akingbade single-family houses over a year in 12in four apartments and
comfort. Local differences29°C and 22average, temperatures between measured temperature and humidityAHunits of g/m
the coastal region were found. On in order to create a database for thermal predicted from outdoor (nearby airport) measurements. In values.
°C were perceived between the subequatorial and indoor air. In winter, indoor3, indoor AH outdoor =(∙0.69+3.2AHwell
between 290perception of the population in Cameroon in humidity above outdoor conditioning condensation of water from
people interviewed preferred temperatures213°C. 28°C and 26buildings ) could be reasonably sources of moisture increase the absolute
conducted a study on the temperature their study, most of the the relationship resulting in a slope <1. During warm humid summer
come to a similar result for Nigeria. In months, indoor absolute humidity is lower than outdoor due to air
only average temperatures, but also diurnal differences play a role. ). Building air condition and occupation flatten
is an important factor in the spread of this disease bymosquitoes. Not to the Boston study, they219found that the outdoor specific humidity (
to the fight against malaria. It has long been known that temperature Nguyen and Dockery Chi Minh City, Vietnam site (29.7°C). Similar
InAfrica, special attention is paid214Paaijmans and Thomas 215mosquitoes. was lowest at the Dublin, Ireland site (19.3°C) and highest at the Ho
indoor-resting mosquitoes transmit malaria faster than outdoor-resting the United States. The mean indoor temperature
indoors and outdoors. This difference is crucial for risk assessment, since Asia, the Mideast, southern and northern Europe, Greenland, and
outdoors depends significantly on the temperature difference between cities from 8sites in 9of outdoorindoor relationships to a set of
found that the ratio of mosquitoes resting indoors and expanded their studySHreasonably well with the indoor
g water/kg air) correlated ,SHwere also observed. For example, the
. However, regional differencesSH or occupant behavior.
Americas |7.1.4 of the most common building types, heating and cooling, occupancy
colleagues) is not necessarily representative
(combined =216US homes in New York ( 60temperature from City (slope =0.36). Their convenience sample (friends, family, and
measuredn Florida ( = ,)20n Roberts and Lay ), Oregon and Washington Athens, Greece site was very similar to that outdoors (slope
20n min intervals; they instrumented =-15year at 1over )20 =0.82) but deviated more at low and high values in Kuwait at the
|
Variations in temperature over time |7.1.5 °C ( of 22.1°C. During winter, the mean thermostat setting was 1.8of
with a standard deviation )541°C (n = 26.6setting was n °C. =2.4
of historical indoor temperatures in the United Kingdom, Vadodaria et al. with a standard deviation ,)733
in the early morning and maximum in the late afternoon. In their review et al. the high end, only 223occurred in the mostly in the morning hours.
sinusoidal daily temperature cycle is typical, with a minimum occurring °C. Active heating26°C and 23were between 8.5%Shipworth
statistics are not provided. Among the studies we reviewed, a roughly °C and at17°C and 10settings, 26% were rather low, between
original data. On occasion, example plots are shown for several days, but . For estimated estimated settings from measurements were on average
diel dynamics although diel statistics could probably be retrieved from the values, but2than self-reported values (21.1°C vs. 19°C on average)
report averages, standard deviations and similar without reporting °C higher the occupants. There was some correspondence between
A minor limitation of many of these studies is that they typically220h. temperature data loggers) and compared with those reported by
18:00–17:0008:00 h and a maximum occurring around –07:00at about settings were estimated from measurements (from
°C with a minimum occurring3Oregon homes cycled over homes. Thermostat 467in 2007in England during the winter of
season and region, the diel temperatures in New York, Washington, and thermostat information through surveys and measurements
°C overnight (00:00–06:00). Averaged over the heating16.7dropped to collected
°C in the evening (16:00–24:00), but19°C and rose to 16.4were )09:00 – Parker224daytime setpoint. Data from a more recent RECS survey
and living room) average temperatures in the morning (06:00 than the settings) of 1.6setback temperature was estimated to be
solid-wall” houses. Overall (bedroom“ 66and spring measurements in °C. During heating season, nighttime25°C and 20.1°C cooler
describe results from winter2164°C. –3- to-peak temperature difference of measured or as determined by self-reported thermostat
with a peak 17:00and maximum at around 06:00around temperatures (either Residential Energy Consumption Survey RECS
andOregon, respectively. InBrisbane, Australia, theminimumoccurs They combine all .2009results for heating and cooling season average
and midnight in Washington 09:00in New York, respectively and 21:00 across ~10 studies, including thermostat results from the US similar.
and 07:00°C, with a minimum and maximum at 4temperature cycled over reviewed heating and cooling temperatures in the United225States
During the winter season, the diel209The results of Singh et al. 204 are available, and the results are
and cooling. In 12Figure be considered only semiquantitative. In
and direct sunlight penetration. As just one example, Filippín et al. based on the collected reports discussed with minimal heating
for more well-insulated buildings, some locations can experience temperatures in different ways, these of indoor air temperatures
strong diel variations especially in rooms with large windows overall reading of the literature and should above. Since authors report
temperatures20exhibited strong diel swings, by as much as a poorly insulated, leaky homeA12Figure Shown in figures represent our
°C in winter. Even likely to be insulated or conditioned; therefore, indoor are representations represents the indoor temperature in
less in northeast India provide some examples of more extreme daily in a home with good heating and cooling. The green bar
dynamics of indoor temperatures. This vernacular housing is them). The orange bar represents the expected indoor temperature
balcony 150from individual homes in a study of 221was <15°C. air temperatures across all regions as a function of outdoor90th and 10
temperature in the city of Santa Rosa, La Pampa, central Argentina. The upper and lower bounds roughly correspond to the of indoor
homes experienced temperatures >40°C when the outdoor th percentiles (directly from literature or inferred from temperature; the
range of >25°C in an enclosed, glazed balcony of an apartment region can vary by ,B12Figure reported for all regions is shown in
measured during winter a diel temperature mean temperatures difference between a –5we show the range same
th percentile home in the90th percentile and 1015°C. The range of
a roughly sinusoidal temperature pattern with amplitude of
Thermostat settings |7.1.6 –1although extremes exist as noted above. The indoor temperature
4°C in a home. A typical home in a region (middle line) will experience
as a proxy where thermostatically controlled heating or cooling we show an approximation of the daily temperature cycle ,C12Figure
are present. The following are a selection across three continents. used for warm and cool seasons.
of direct temperature measurements, thermostat settings may be
In the absence
understand energy use, behavior and demographics, Chen et al. 7.2|Non-residential air temperatures
In a survey intended to better222summer, the mean thermostat
used for heat in winter; 20% of respondents used electric heating. During air was conditioned in winter and summer. Mendell and Mirer
survey, 75% reported using air conditioners. Air conditioning may also be Evaluation (BASE) Study. Most buildings were mechanically ventilated, and
noted that most residences in this region used air conditioning; in their U.S. Environmental Protection Agency's Building Assessment Survey and
hot in summer (29°C mean) and cold in winter (4°C mean). They metrics, indoor air quality, ventilation, and occupant symptoms during the
during summer and winter in Hangzhou, China. This region is considered ~100 United States office buildings were studied in detail for thermal
collected thermostat settings from participants ,1998and 1994Between 226reported that

| 60of 23
2 1F I G U R E with good heating and cooling.( 40

( A)
th percentiles. The orange curve represents
35
the expected indoor temperature in a home
CoIndoor temperature
90th and upper10the approximate lower 30
air temperature vs. outdoor air temperature
25
for all regions reviewed. Black lines enclose
A) Indoor 20
ranges across all regions th and upper
15
local cool and warm seasons indoor temperature
10
uncond itioned
th percentile homes. (C) Mean90reviewed for the
conditi oned
10home (middle curve) with enclosing lower
5
in a poorly insulated, leaky home - 15 - 10 -5 0 5 10 15 20 25 30 35
heating and cooling. (B) Daily temperature
CoOutdoor temperature
indoor temperature cycle for typical with minimal
The green curve represents the indoor
35
Indoor temperature (range varies)

( B) ( C)
30
CoMean indoor temperature

Warm home in region
5-15oC
25
1-4oC 20
15
Cool home in region 10
5
0 6 12 18 24 Warm Cool
Time of day (h) Season
summertime temperatures were associated with decreased symptoms. 7.3|Indoor surface temperatures
this was mostly associated with higher wintertime temperatures. Higher
nose, were associated with higher temperatures over all seasons, and more than those in a well-insulated building during a pleasant spring day.
to note that “building-related symptoms,” such as cough and runny during winter or summer will deviate from the temperature of indoor air
was higher in summer (47.3%) than in winter (27.3%). It is interesting wall surface temperatures in poorly insulated buildings
recommended for comfort in summer. The median relative humidity floors are more influenced by the outdoor thermal environment. Outer
noted that summertime temperatures were mostly colder than the range indoor temperatures do not change rapidly. Outer walls, ceilings, and
°C and a similar range, 21.6–24.3°C, in summer. They24.8to 21.6from in contact with warmer or cooler surfaces, this may be reasonable where
wintertime temperatures ranged with indoor air. For furniture and other items that are not sunlit or
California, researchers observed temperature (and other–6factors) for obtained by simply assuming that the surfaces are in thermal equilibrium
8 h on a single testing day in summer or winter. buildings in A first-order estimate of the indoor surface temperature can be
varied by only 37In a study of 227degree swings. 10greater than
experienced much larger ranges, sometimes buildings, temperature flux balance across the inner surface of a building's outer wall; a
degrees over the testing 2or 1commercial period, but others more detailed discussion of the thermal environment as it relates heat
the buildings tested. For some ranged from 27°C to 14ranged from to mass transport of gases and particles is found in Section
°C. During winter, indoor mean temperatures28°C to 23°C across wall surfaces can be obtained by performing a simple steadystate
Summertime mean temperatures likely to occur at indoor ), through an outer wall is given by8.
The Thermal Comfort Database II228temperatures as shown in Sṫeady-state flux,
wall W/m(2An estimate of the range of temperatures
temperatures in office buildings and schools (among others included equation(59),
in the database) fall within a broad band, increasing with outdoor

( )
not collected and instead are related to monthly average ̇ (59)
wall=h wall ∙T surf,out −T surf, in
determined from meteorological stations or similar. Despite commonly

these limitations, the measurements demonstrate that indoor values wherehwall is the conductive heat-transfer coefficient for the wall (W/ (m2
that are paired with thermal comfort measurements, and therefore K)),∙Tsurf,out temperature of the outside surface of the wall (K or °C), and
not continuous or comprehensive. Outdoor measurements were is theTsurf,in through a wall or glazing is sometimes given the symbol
of thousands of measurements, during occupied periods, across inside surface of the wall (K or °C). The conductive heat-transfer coefficient
many building types and climates. These are spot measurements is the temperature of theU; its reciprocal is often given the symbol R /U. =
is a rich source13Figure. 1
|
Offices Schools 13F I G U R E Worldwide spot

40 40
temperature based on data available
35 35 from the Thermal Comfort Database II outdoor
Indoor air temperature (oC)
Indoor air temperature (oC)

temperature as a function monthly average
30 30
measurements of indoor228
25 25
20 20
15 15
10 10
5 5
- 10 0 10 20 30 40 - 10 0 10 20 30 40
Outdoor monthly average temperature (oC) Outdoor monthly average temperature (oC)
The heat flux between indoor air and the inner surface of the of building materials that dampen dynamic changes in temperature.
all,ẇair surf−, is given by equation (60), environment will increase wall surface temperatures. Also, this
steady-state analysis does not account for the buffering effect
( )
̇ (60) radiant temperature of the indoor
airsurf−= h air surf−∙T surf,in −T op
sensors due to variations or uncertainties in surface emissivities.
wherehsurf-air between the inner wall surface and indoor air and than continuous data, and may not be as accurate as contact
is the heat-transfer coefficient associatedTop heat-transfer coefficient, of the camera, but thermography usually provides a snapshot, rather
assuming the air and mean radiative temperatures are close in value). The generates spatial temperatures, limited only by the resolution
is the operative temperature of the indoor environment (andhsurf-air only represent a very small area of a wall. Thermography
is the sum the convective heat transfer, ,hc, and radiative heat transfer,h are more accurate and can generate detailed temporal dynamics, but
radsimplified linear radiative heat transfer. According to temperatures are uncommon. Investigators have measured indoor
, components, assumingequation (61between indoor air and wall surface. surface temperatures using direct contact sensors (thermocouples
convective heat-transfer coefficient depends on the temperature gradient and thermistors) and by use of thermal imaging. Contact sensors
), the229,230 Field measurements of indoor surface
Peng and Wu231for determining heat flux and thermal insulation
| |0.32
c= 1.78 ∙ |T|surf,in −Top| | (61) for developing methods home and made measurements during
They report .2001and 2000results from a single day as typical, mainly
instrumented walls in a singleR highest value was for the roof.
as a constant, between the inner wall and indoor air. When setting °C. The69.2°C to 27.9the same walls/ceiling, ranged from
K).∙W/(m² 5.5230The radiative heat-transfer coefficient is taken °C, whereas outdoor surface temperatures, for25.6°C to 23.5
steady, state, the heat flux through the wall is equal to the heat flux values. Indoor surface temperatures covered a narrow range, from
Atequations (59) = (60) and combined with (61), equation (62 Walikewitz et al. ,2013weeks in August-September of 2For 232m
) is obtained. the Geography Department of Humboldt University in Berlin. A large (>20
( ) surface and air temperatures for all four walls in each of four rooms in
( ) | |0.32 ( )
wall∙T surf,out −T surf, in = 1.78 ∙ |T |surf,in −Top| | + 5.5∙T surf,in −T op measured2°C and the distribution varied by time of day.10range of up to
by <1°C across the wall. Other walls exhibited a temperature

(62)
showed that some walls were very uniform in temperature, varying
and cooler than indoor air over night. Thermal infrared camera analysis
coefficient, 14Figure are the results of solving equation (62) forT day (8–9.4°C in three of the rooms) and was warmer than air at midday
surf,inwith Top °C, 25set to Tsurf,out Shown in °C. The wall heat-transfer window wall had the highest temperature amplitude during the
35°C to10varied from −hwallW/ (m 0.1is set to values reflecting ,2W/(m °C from one another. The3non-window walls deviated by as much as
K) (well insulated), 2∙2surfaces (like occupants) that increase the mean during most of the evening to early morning hours. During midday, the
surface temperature and, for this range8of conditions, varies by about °C of the indoor air temperature1walls, temperatures were within
°C. Note that the presence of warm influenced by the outdoor among walls that varied over the day. For the three non-window
imposed on the structure. A poorly insulated wall is more wall.” Contact sensor measurements revealed temperature differences
air temperature for a well-insulated wall, deviating by less than ) window was present in each room and comprised most of the “window
°C1over a very wide range (45°C) of outdoor wall surface temperatures

inner surface of an outer wall will more closely follow the indoor Hulm and Doran233England. While they did not provide temperature
K) (poorly insulated) and values in between. As anticipated, the∙ studied thermal performance of “solid” walls in residences in
| 60of 25
14F I G U R E wall temperature conditions 28

wall for a variety of insulation and outdoor
27
indoor surface temperature of outer
,o C
Simulated
26
surf,in
25 T op
hwall W/m 0.1 =2/K
indoor surface temperature,T

24
23 hwall W/m 0.5 =2/K
22
hwall W/m 1 =2/K
21
20
hwall W/m 2 =2/K

19
18
- 10 -5 0 5 10 15 20 25 30 35 40
outdoor surface temperature,T
surf,out
,o C
22°C.–20°C. A picture on the wall was about 18the coldest spot about B15Figure °C cooler or hotter than indoor air.6temperatures
of “unusually uneven” temperatures26curtains) of about much cooler. Both the kitchen floor and kitchen window experienced
for an indoor temperature (and of thermography. In an example above bare ground in a crawl space) was often were cooler by
°C, the wall temperature is cooler, with across a wall they found that 1 °C during the measurement period. The kitchen1floor (uninsulated
data in their report, they did show some results °C of the bulk air. The dining room window, kitchen wall, and floor
kitchen, as well as outdoor air (in the shadow of a house eave). between a sensor location and dining room bulk air. The dining
window, a south-facing wall, ceiling, and floor. Measurements were room floor, ceiling, and wall temperatures were typically within
also collected on the floor, a south-facing window and wall in the between surface and indoor air is shown in direct sunlight.
room in air, a south-facing foil tape and data collected at plots for the instantaneous temperature different on the difference
min intervals. Measurements 5were collected in the dining The influence of the outdoor temperature 16Figure shows box
thermocouples were attached to surfaces with aluminum least double-paned, deviates rather greatly from indoor air, strongly
years old and many are showing signs of failing seals. Type 20K influenced by outdoor temperatures, and probably occasional being
cooling. The conditioned basement is approximately the width of the entire range of outdoor temperatures. The window, despite
of the home, and there is an unconditioned crawlspace underneath - insulated ceiling is very close to the indoor air temperature across
at the kitchen and living room. The ceiling and walls are insulated, and and the dining room ceiling. The temperature of the well
2/1the attic is unconditioned. Windows are double-paned, but for the kitchen floor, window
Carolina, USA. The building uses central air heating and building is a 17Figure with being more influenced by the outdoor temperature.
in Chapel 1960story home with a basement built in -1Hill, North dining room and kitchen windows histograms are broader and consistent
.2021 ,1ending June ,2020 ,12months starting on December 5.5 histograms resemble the indoor air temperature histogram, but the
this literature somewhat, one of the authors of this review measured °C. Indoor surface temperature30°C to greater than 5from less than −
The indoor surface temperatures in several locations in his home for °C and ranged20often open. Outdoor temperatures averaged about
To broaden evening; during temperate weather, the thermostat was off and windows
Shown in15Figure over the entire time period of measurement. °C in the18°C during the day and 21thermostat typically was set to
A and B are box plot results from each locationA 15Figure uninsulated. °C while away. When home, the17days and had set the thermostat to 10
because the kitchen is above an unconditioned crawlspace that is also distribution because the homeowners were away from the home for
in the kitchen tended to be slightly cooler than the dining room, possibly from each location. Note that the indoor temperature exhibits a bimodal
the lowest and highest temperature of surfaces examined. Surfaces shows histograms of temperatures
°C) and experienced35exhibits the largest range of temperatures (about °C or more.20measurement, surface temperatures can vary by up to
°C range. The kitchen window15surface temperatures lie within a and warmer in summer by several degrees Celsius. Over the period of
the interquartile range away from the top or bottom of the box. Most and surfaces facing uninsulated cavities are cooler in winter
times 1.5points not considered outliers. Outliers are defined as points are usually within a few degrees of the indoor air temperature. Windows
th percentiles; the whiskers reach to the most extreme75th and 25the th century home in the United States. Surface temperatures20typical, mid-
from different locations. The upper and lower limits of the box represent one home, there are several observations that are likely generalizable to a
shows temperature Although this is a very limited study of

|
( A) ( B) 8 in 5 1F I G U R E are shown in(

two indoor air locations. Dining
30 (DR) and kitchen (K) locations air, and

6 different surface locations, outdoor 7room
plot of instantaneous temperature (Δ16
25 FigureA) Box plot of temperatures measured
4
; (B) BoxTbetween location and indoor air
20 ) differences
oC
oC
2
surf,in
location air,in
15
T-
Tempera ure,T
10
∆T =T
-2
-4
0
-6
-5
-8
K ll
R R c or
id
D ar
ts ling
id ll
e
ai w
w or
w
a
a
D tsid
rm
do
e
flo
do
w
l
flo
or
w
ou e w
ng
or
al
w
al
rn
ou ei
do
e
flo
do
in
w
in
flo
ou
w
ili
R
ai
id
w
in
ce
de
in
de
K
ts
R
R
K
R
w
D
w
R
si
R
i
D
D
ts
K
R
t
ou
ou
aq
D
K
D
t
K
R
da
location location
7.4|Museums and cultural heritage therefore recommends keeping the temperature
interval constant enough to stabilize the relative humidity. humidity. Thomson
cause difficulties in the definition of climatic nominal values. large fluctuations in temperature and Visual Arts in Norwich, UK.
objects, for example, objects made of wood and metal, can therefore As a rule, the goal is not to set a specific236room climate, but to avoid
changes of hygroscopic materials can lead to tension cracks. The masonry. The desire for transparency and flexibility in the exhibition
differing behavior of discrete material types within composite rooms is prevalent here. One example is the Sainsbury Centre for
an important topic. Non-ideal conditions can result in changes with large glass areas while simultaneously reducing compact
the size and shape of materials, trigger or accelerate chemical been architecture prefers to create light-flooded buildings
reactions or induce biological infestation. In particular, volume in the restructuring or extension of existing museum buildings, modern
of rooms in which cultural heritage items are stored has always indoor climate. In contrast, modern buildings can exacerbate climatic
The environmental control234 or in variability, due to contemporary-aesthetic demands on the building
the literature are oriented primarily on the moisture properties of structure and its interior design. In the construction of new
the respective material category, but also on human well-being. in few glass panels can ensure a stable for the indoor climate.
values or recommendations which are to be found Buildings with compact, multiple240- layer masonry and
have served to define conditions that minimized damage. Guideline should enable the building itself to be an experience, can
possibilities and the local climate than on research which would be associated with significant negative consequences
originally based more on technical first published by Thompson, The pursuit of a spectacular architecture, which
Acceptable ranges of temperature235and relative humidity were to churches, which are often not heated at all or only temporarily.
for certain indoor climate ranges in museums were sometimes extremely changing outdoor climate. This particularly applies
are given by Stolow. 236 65%–40%24°C and –19generally recommends alsohistorical buildings are endangered by a constantly and
whoRHNonetheless, Camuffo et al. .237Recommendations materials Not only theworks of art themselves, but 18Figure .2013 ,1to June ,2011
for inhomogeneous horizontal and vertical temperature distribution and ,10in Roggersdorf, Bavaria during the period from December
certain by humidifying systems that emitted too much moist air. Ranges and relative humidity in the unheated church of St. Margaretha
the relative humidity in rooms with collection items made of shows the scatter diagram for temperature241sites of the State of Bavaria.
unsatisfactorily by creating a very found in Schieweck and Salthammer. of frost in winter. Similar results were found in other cultural heritage
showed that air conditioning238systems in museums often work % as well as strong short-term fluctuations. In addition, there are periods
for climatic conditions in museum collections can be 78a consistently high level of relative humidity with an annual average of
Further compilations of recommendations239 The indoor climate is characterized by242It is

| 60of 27
6 1F I G U R E temperature (Δ
The instantaneousToutdoor temperature
air as a function of the instantaneous
the dining room ceiling, kitchen
floor or kitchen window and indoor between
) differences
( °C)
Dining room
ceiling
Outside temperature (°C)
17F I G U R E Temperature histograms. (A) indoor and outdoor air, (B) dining room surfaces, and (C) kitchen surfaces
|
in wall cavities of prefabricated houses. of the cavity.

air flows through an “effective leakage244,245of pentachlorophenol
more penetrations through the wall, air building models assume that
pathway that can include the full volume area” that acts as one or
which result from the microbial degradation follows a more complex
to temperature gradients. Pressure gradients induce infiltration
through the building envelope and into buildings. While many due
This happens when water condenses in the cavities246wall cavities.
gradients will also induce flow through external and internal
Internal temperature and pressure
emissions and indoor air quality. For example, Poppendieck et al.
uncertain. There is evidence that varying outdoor temperatures influence
extent to which this influences indoor air quality or is predictable remains
between the occupied and unoccupied spaces occurs, but the

18F I G U R E Indoor climate in the St. Margaretha Church in
Therefore, air communication247pentanediol monoisobutyrate) were -1,3-
The figure was taken from reference .2013 ,1to June 2011,10
trimethyl-1,2,4/O) of compounds specific to interior paint (isomers of
of relative humidity and temperature for the period from December
diagram shows the hourly mean values University of Bamberg °C. They also observed that (I22°C to 0from 5to 2increased by a factor of
Roggersdorf, Bavaria, without temperature241control. The scatter building envelope such as insulation, wood, and the vapor barrier. The I/O
with the kind permission of Prof. Ralf Kilian, Fraunhofer IBP and of these VOCs were likely associated with materials found in the
operated by the National Institute of Standards and Technology). Some
temperatures, in a test house (the Net Zero Energy Residential Test Facility
even greater negative impact on the condition of historic buildings. increased with outdoor temperature, despite a constant indoor
to be expected that the effects of climate change will have an concentration to the outdoor concentration of many VOCs (I/O) reliably
observed that the ratio of the indoornot by outdoor temperatures.
influenced
7.5|Temperatures in building microenvironments operating temperature/conditions, and implications.

of this review; instead, we will discuss several common systems, their
.)27 ,4is present (see ASHRAE Handbook - Fundamentals, Chapters and sinks of heat energy are climate control systems and those used
such as wall cavities, ducts, and crawl spaces will tend to lie between for cooking. The range of heat-transfer systems is beyond the scope
the temperatures of adjacent spaces unless a heat source or sink Among the more intense, but localized, artificial sources
contribute substantial surface area to a building. Air communicates closer to cooking temperatures of ~300°C or lower under normal use.
between the main living area and these spaces, but the conditions nearby stovetop surfaces. Pans and utensils will tend to remain
may be very different. The temperature of microenvironments °C, heating2000~800–1000°C. Natural gas flame temperatures approach
spaces, and attics can constitute a sizable volume and heating elements that are visibly red have a surface temperature of
Microenvironments such as wall cavities, ducts, crawl182in summer. °C although some can go higher. Electric burners and broiler260of about
60in temperatures near ambient in winter to greater than under normal use. Most residential ovens have a maximum temperature
°C subject to direct radiative heating or cooling of the roof, resulting will range from ambient temperature to their maximum temperature
attics of many buildings are independently ventilated and and the cooking implements (pans, utensils) themselves. These surfaces
or seasonal temperature dynamics relative to the inner surface. The surfaces include ovens, stove-top burners and surrounding surfaces
to outdoor temperatures, thereby experiencing temperature swings Cooking248–254the thermal formation of NO and NO
due to direct solar heating, radiant cooling, and daily temperature in the indoor environment resulting from bas burners, candles, etc., is
of the outside panel of an insulated wall cavity will be much closer An important aspect of elevated temperatures2nitrogen and oxygen.
temperatures243varying from far below freezing to very hot. from atmospheric255
The temperature the envelope of an occupied building can experience used to control indoor air temperatures during the cooling season
Therefore, some materials and their surfaces within °C (water-based radiant panels) to2000°C (combustionheating). Surfaces
unpleasant phenomenon is the perception of chlorinated anisoles, 70temperature of the heat-transfer fluid can range from below
wall cavities can also be detected by the odor of microbial activity. Another fluidbased heat pumps, and radiant panels. For fluid-based systems, the
the odor emitted from an animal that has died in the wall. Mold present in coils, combustion (gas-and oil fired) heat exchangers, heat-exchange
wall cavities can influence indoor air quality; many of us have experienced during the heating season include hot-water radiators, electrically heated
enters the occupied volume of the building. It is perhaps intuitive that or cooled surface. Surfaces used to control indoor air temperatures
among them is whether the air in contact with those materials regularly relies on radiative and convective heat transfer from a heated
gradients on indoor air quality will depend on many factors, chief to, or from, air to heat and cool to the desired temperature. Generally, this
The impact of these temperature Climate control of air in buildings requires energy transfer
| 60of 29
cooler (when warming) than the underlying heater core or working fluid. air movement, increasing transport rates especially over surfaces.
surface in contact with air will be both warmer (when cooling) and gradients result in convective
in service. However, for heat to transfer appropriately, the heat exchanger
temperatures of the air-side of these heat-transfer surfaces while
our literature search, little information was available on measured 8.1|Diffusion (solid materials, particles, and gases)
°C or lower for specialty applications. In0can operate down to
°C, but the fluid in the expansion region of synthetic refrigerants10below enabled by diffusion is proportional to the diffusion coefficient,
be incorporated into radiant panels. Chilled water systems can operate rapid collisions with other molecules and more rapid diffusion. Transport
exchangers (cooling coils) and heat pumps. Chilled water pipes can also mean kinetic energy of a molecule increases, resulting in more
include chilled water or refrigerant-based heat is driven by random molecular motion. As temperature increases, the
as has been observed for heated surfaces and during cooking. Diffusion through a homogenous mediumD“Fickian” diffusion is given by
time after a long period of time. Heating of deposited materials concentration gradient driving force. Flux in the x-direction resulting from
generates aerosols and increases air concentrations of SVOCs first , and theequation (63), where C of the diffusing molecule in the medium.
an entire building, very high temperatures could result in chemistry is the concentration
the that is, sometimes, relevant to indoor air quality. One well-known
example is the odor generated when turning on a heater for dC (63)
lux = −D∙
dx
to be to achieve the necessary heat transfer. While the surface
area of heat exchangers is small relative to exposed surfaces in needs as its area-normalized emission rate, for example with units g/m
smaller the surface area AC operation in several studies. Flux at the exposed surface of an indoor material is the same2/s.
In general, the249,250,253,254,256–258hotter (or cooler) the surface, the
responsible for the removal of polar gases observed during
Cold heat exchanger surfaces, covered in condensed water, are259,260 Diffusion in air |8.1.1
than indoor air), the shorter the time interval at that temperature.
systems, the greater the temperature deviation (cooler or warmer simpler semiempirical model of molecular diffusion coefficient of species
a few above as examples. As a rough generalization for heat-transfer on temperature and a temperature-dependent collision integral. A slightly
to achieve the desired supply air condition, and we only noted theory results in an expression for gas diffusion coefficient dependent
are a wide variety of methods, fuels, cooling fluids, etc., applied rate molecules can transport to and from that surface. Chapman–Enskog
is common to cool air to remove moisture, then reheat for comfort. There diffusion is the primary transport mechanism and limits the
of supply registers, and many other factors. In commercial buildings, it In the slow-moving air over indoor surfaces, gaseousi air is given by Baum
the conditioned space. However, these can vary with climate, location in261and applied by others to indoor transport analysis,
°C but cools somewhat prior to entering50can raise air temperature up to

√
°C above desired room temperature. Residential combustion heaters10 10−7 ⋅T 1.75 ⋅ 1
+MW
1
airMW i
the higher end more typical. Supply air for heating is commonly about air,i = ( )2 (64)
P⋅V 1∕3air
+V1∕3
°C, with13°C to 6less than a minute. Supply air for cooling ranges from i
or lowered temperature for seconds or tens of seconds, but generally
velocity (5 m/s) and duct length (tens of meters), air is at its elevated air and speciesair andMWi weights of air (mean) and the diffusing gas,
system. In a duct, after passing the heat exchanger and given the typical are themoleculariand ,Vair and Vi whereMW molar volumes of
periods (<1 s) of very low or very high temperatures depending on the are thei example, the small molecules that make up air (O
relatively short. Above heat-transfer surfaces, air is subjected to very short in air for molecular contaminants of interest is relatively narrow. For
that air spends at temperatures other than the occupied space is usually The range of diffusivities .2N ,2H ,2O, Ar, CO210·1.5in the range of
The elapsed time of SVOCs, with molecular weights upwards of ,−5 10·2to −5m 210·0.4
g/mol, are about 400etc.) have diffusivities at room temperature
/s. The diffusion coefficients−5m 2°C.35°C to 15increases from
8|TR ANSPORT PHENOMENA as temperature 12%diffusivity in air will increase by only
the typical range of indoor temperatures. For example, molecular
rapidly transports contaminants throughout indoor air. Thermal /s. Temperature dependence of diffusivity is relatively weak over
increasing temperature. The bulk movement of air, or advection, more
is known as diffusion, and the rate of diffusion generally increases with
from a higher concentration region to a lower concentration region. This Non-porous materials |8.1.2
air, random motions of molecules result in net transport of a contaminant
materials that are essentially static, like a paint film or a quiescent layer of draw a distinction between these categories, somewhat arbitrarily, at
through indoor environments follow well-established mechanisms. In and non-porous materials describe a continuum from textiles
The movements of molecules to glass. In between, materials may have elements of both. We Porous
|
even though complex polymer matrices may in reality be nanoporous. carpet fibers and other materials. Berens and Hopfenberg269et al.
homogenous polymers that we consider “non-porous” for rubberypolymers, however, arequite small. As anexample, Barrer
may also change over time, as in a drying paint film. averages of their data). The activationenergies reported
polymers, presence of plasticizers, and the size and concentration of kJ/mol, respectively (our 82and ,92 ,56and reported activation energies of
the diffusing molecule. Diffusion may vary spatially in heterogenous in polystyrene (PS), poly(methyl methacrylate) (PMMA) and PVC
materials. Under some conditions, especially at high concentrations studied diffusion volatile organic compounds270and Ferry
of the diffusing substance, diffusion may not be Fickian. Diffusivity /mol for diffusion coefficients of alkanes in silicone rubber. Similarly, Chen
limiting factor for emissions of low-molecular weight compounds like kJ 17measured a typical activation energy of about 263Krauss and Spinks
VOCs. Diffusion coefficients are dependent on the structure of the energy for self-diffusion of a range of organic liquids reviewed by
“wet” coatings are non-negligible and are often the activation energy is similarly small for liquids. For example, the activation
be considered negligible for contaminants of interest in most indoor kJ/mol. The 60kJ/mol to 17of natural and synthetic rubbers to range from
environments. Diffusion rates within plastics, resins, rubbers, and observed activation energies for the diffusion of n-hexadecane in a variety
than for gases. Diffusivity within materials like glass and metals can 271exhibit Arrhenius behavior, such as for carboxylic acids in polystyrene,
coefficients vary over many orders of magnitude within polymers.262 kJ/mol at room temperature. In some reports, diffusion did not 20is about
Diffusion coefficients within non-porous solids are much smaller 272observations are usually for very high concentrations of permeants.
ranging from263,264For example, Berens 265g/mol; 32methanol (MW = but these
Diffusion of magnitude in hard, nonplasticized PVC, for VOCs is times. In silicone rubber, the increase is only about a factor of
observed a decrease in diffusivity over approximately four ordersD m hard we will discuss later, the dependence of diffusivity on temperature
the ~10−15m 2g/mol; 86/s) to n-hexane (MW = Dm ~10−19m 2and Ferry becomes relevant for emission rates of small molecules (e.g., VOCs) from
g/mol). In plasticized PVC flooring, Cox et al.263 10coefficients in depends plastics. The emission rate of larger molecules (e.g., SVOCs)
observed diffusion−11m 2/s). For a variety of rubbery polymers, Chen coefficients. limited by gas-side mass transfer, not internal diffusion, and
= 226g/ mol) and n-hexadecane (MW = 170for n-dodecane (MW = As .1.5much more on equilibriummaterial-air partition
/s range266g/mol; 92that the diffusion coefficient of toluene (MW °C is estimated to increase diffusion coefficients by about nine35to
/mol; Dm ~7·10−13m 2larger than n-pentadecane ( 10a factor of (8015kJ/mol) in hard plastics, an increase in temperature from
/s) wasMW g/mol; = 212Dm ~7·10−14m 2/s). Meininghaus et al.267observed °C a middle value for the reported diffusion activation energies
g 114much higher diffusivities in PVC flooring for octane (MW = Using
et al.Dm = 6·10−9m 2g/mol; 88/s) and ethyl acetate (MW = Dm = 8 ·
10−9m 2reported in most non-plasticized polymers. For example, Ramirez
as wet paint, adhesives, and thin fluid films, is generally higher than Porous materials |8.1.3
material, such paint films and calculated an initial diffusivity of
. Diffusion trimethyl-262 10·4with homogenous wet or fluid-like condensed is common to lump complex pathways into a single “effective” diffusivity,
pentanediol monoisobutyrate (TMPD-MIB) from fresh-1,3/s) by more complex pathways. In many areas of environmental research, it
-2,2,4studied the emission rate of−9m 2as it dried. 50by a factor of paint films. The net transport of molecules through such materials occurs
/s; the diffusivity decreased much air as fiber, and even some materials not obviously porous like dry
temperature dependence of diffusion coefficients in polymers has composed of compressed powder and binders, textiles that comprise as
been conveniently characterized using the empirical Arrhenius forms including wood with a regular pore and void structure, gypsum
Theexpression (65). phase interspersed with air-filled voids. These materials take many
Porous materials in this review are characterized by a condensed material
EA Deffthat the mathematics of transport are consistent with Fickian diffusion.

nk =A− (65)
R∙T to, and absorption into the material. Also, it is often assumed
that accounts for porosity, tortuosity, adsorption ,12,267,273–275by
EA is the activation energy and A approximation since the factor Therefore, flux can be describedequation (63), where D is replaced by Deff
number of collisions. The Arrhenius equation is an processes. Meininghaus et al. .267
is the pre-exponential factor that describes orientationA and the air itself, suggesting little transport resistance through these porous
of monomolecular chemical reactions. However, it has been shown paint. materials. On the contrary, the VOCs had much lower effective
that the relationship can be used for many chemical and physical diffusion coefficients in a more solid concrete and acrylic
was originally derived to describe the temperature dependence diffusivity of two VOCs through carpet, aerated concrete, brick, and
is also temperature-dependent. The Arrhenius equation gypsum were very high and approached diffusion coefficients in
For example, Welle and Franz26810 observed that the effective
/mol inpoly(ethyleneterephthalate) (PET)withdiffusioncoefficientsofapproximately purposes of this review, a more useful model retains the simplicity of
solvents (acetaldehyde, benzene, andtetrahydrofuran). Theserangedfrom76to107kJ influence of temperature on transport through these materials. For the
reported activation energies for the diffusion coefficients of three−19 10to −15m 2into but hides the mechanistic details that are important in understanding the
/s. PET is used in plastic bottles but also recycled The effective diffusivity is handy for many applications
| 60of 31
characterized by pores of various sizes) and following a tortuous path, air and indoor surfaces, the steady-state flux is proportional
molecules transport mainly by diffusion through void spaces (perhaps to a concentration gradient and a mass-transfer coefficient, between
that act to slow diffusive transport. One such model assumes that analogous, but not identical, to heat transfer and similar correlations
Fickian diffusion but introduces themainmechanisms275,276 can be applied to derive mass-transfer coefficients. For transport
but can adsorb, absorb,277,278react with the surrounding solid material. Mass transfer is .7.3and 5.3introduced in several sections including
or even279–281For this model, the effective diffusivity can be defined as heat transfer associated with thermal gradients have been
Correlations describing conductive and convectiveh.
∙Dε ( )
eff= (air ) (66) = luxh ∙C surf −C bulk (67)
τt ∙ 1+Kp
where τt is a tortuosity parameter, ε is the porosity, and Kp concentration ( Csurf contaminant in the air adjacent to the material surface, and
with thermodynamic parameters such as vapor pressure, vapor saturation fluid-mechanical boundaryCbulk layers). The mass-transfer coefficient,
at the microscopic scale. Partitioning to materials generally correlates is the concentration of a of the room (e.g., excluding near-surface
that the entire volume of material equilibrates instantaneously, only in the bulk room air. The latter is sometimes defined as an average
rapidly resulting in local equilibrium. To be clear, this does not assume room concentration or as the average in the well-mixed portion
the porosity. For thismodel, adsorptionandabsorptionareassumedtooccur molecules and particles.has the transport limited deposition velocity,
between air and the whole material, which must be modified by is also known ,vtis the concentration uptake like surface-reactive
that this partition coefficient differs from that describing partitioning when referring to species that experience net ,
of the surrounding material and absorption into that material. Note Cano-Ruiz et al.283derived equation (68from Nazaroff and Cass
of voids. The partition coefficient accounts for adsorption to the surface ) (following284,285for laminar convective flow over a flat plate.
length molecules must take to traverse the material through the network ) for the length-averaged mass-transfer coefficient
is a partition coefficient. The tortuosity accounts for the increased pathCg*
( ( ) 1∕4
), and/or the octanol-air partition coefficient (KOAexperiments. Algrim et al. )0.463
D g∙β∙||T
f sur−T ∞||∙H3
h≅ 0.67 ∙air∙ ∙ (68)
nice demonstration of this effect is evident in a recent and elegant set of H Dair 4∙ 2
air
). A274 10carboxylic acids in latex paint films; these values ranged from
measured the effective diffusivity of n-alkanes, 1-alcohols, 2-ketones, and−
13m210/s to −12m 2/s and observed that Deff correlated with Cg*coefficient. H10∙indoor space (~2 m), α is the thermal diffusivity of air (1.9
Partitioning to textiles also increaseswith the octanol-air partition .136,282 of thermal expansion of air (β = −5m 2/s), g due to gravity (9.81 m/s
is the acceleration2T/1is a characteristic height of an the coefficient
for higher molecular weight molecules because both processes tend ), β is∞for an ideal gas), Tsurf is the surface temperature, T∞
to have much higher effective activation energies (see Section the temperature outside the boundary layer (or in the “bulk” air), and
of indoor temperatures under normal living conditions. However, the isνair 10∙is the kinematic viscosity of air (1.6−5m 2- Ruiz et al.
effect of temperature on adsorption and absorption is much larger h dependent on the temperature difference (to the ¼ power). Cano =
influence of temperature on diffusivity in air is small over the range temperature difference between opposite walls was 25/s at 283estimated
As noted above, the4the solid/condensed portion of the material. 1.6·10−4K. 4°C). We see here that mass transfer is weakly the
transport through porous materials (of SVOCs in particular) is to nitrite coated filters in an office and apartment was-2in
dominated by its influence on equilibrium partitioning with on ozone deposition to surfaces of a room-sized enclosure deposition
). Therefore, the influence of temperature dimensional simulations of laminar convective flow where m/s for
(e.g., the central tendency for ozone with building surfaces.
This is smaller than indicatedh ~ 1·10−3m/s), 286from field measurements
8.2|mass transport that other energy inputs to flow indoors can be more important
Thermal gradients, convection, and than thermal gradients for gas-side mass transfer associated
suggesting
the rate that molecules and particles are transported to and from surfaces. ozone again for comparison, measured and modeled values of
skin. Convection increases bulk transport through the room, but also increases transfer to the occupant surface than to a typical building surface. Using
rising air that influences the rate contaminants can deposit on our clothing and in a higher meanmass-transfer coefficient associated with contaminant
than the surface of our bodies, we are surrounded by a convective plume of W incandescent lightbulb or fan). Convection in turn results100W (e.g., a
that is slightly less dense than the bulk room air. Since room air is usually cooler 100induces flow in the space equivalent to an energy input of roughly
can then warm the air near its surface, inducing upward convection of air in strongly stable convective flow around the body. The energy input
that are at a different temperature.Awall warmed by incident sunlight thermal gradient between occupants and the surrounding air can result
gradients arise from heat transfer between airand nearbysurfaces Theh 10·2range from −4 10·5m/s to greater than −3m/s. 287–292exchange
in air result in density gradients that induce advective transport. Usually, these resistance to uptake or emissions, greater rates of gaseous contaminant
Temperature differences In the absence of significant surface

|
building surfaces after accounting for differences in surface area. an important role in deposition/resuspension mechanisms. Qian et al.
air most convective flow regimes can be found in Nazaroff and Cass. and temperature cannot be derived. However, humidity also plays
are expected between air and occupants than between significant influence, so that a simple relationship between resuspension
with that side of the particle, have more kinetic energy on average at higher temperatures, but the microscopic surface roughness also has a
than molecules colliding with the cooler side. A detailed treatment the binding forces decrease298to the substrate. Busnaina and Elsawy
of temperature gradient-driven deposition in natural and forced state that condensation increases the adhesion of particles299force.
than diffusivities of gases. They also experience thermophoresis, or substrate, creating a capillary force that increases the overall adhesion
the tendency for particles suspended in air to move toward cooler a humid environment, water can condense between the particle and the
regions. This is because molecules on the warmer side, colliding come to similar conclusions. In
are much lower since their Brownian diffusivities are much lower
in deposition rates for particles. For284,285 0.3example, for
Mass-transfer coefficients for particles can result in dramatic changes 9|HUMIDIT Y INFLUENCE INDOOR CHEMI STRY,
2 ·10µThey predicted that relatively small temperature gradients0.001 IONS , AND PARTITIONING
°C warmer than bulk room air, the mass-transfer coefficient is only HOW TEMPER ATURE AND EMI SS
that is coefficient is more than three orders of magnitude higher with −6
10·2.5m diameter particles depositing on a vertical isothermal wall 9.1|Gas-phase reactions
°C cooler than room air, the masstransfer2m/s. For a wall that is −6
at surfaces can influence long-term deposition of particles As noted early on by Weschler and Shields,300chemistry.
that contribute to the development of surface films and soiling. gradients ozone reacting with NO and selected terpenes. Some
to masstransfer coefficients of gaseous contaminants, temperature the contrary, are relatively slow but can generate including
m/s. While these values are still small relative at rates that may have exposure consequences, such reactions, on
s.1990season, has been intensively investigated since the early as formation of ultrafine particles from ozoneterpene products
of indoor surfaces, which occurs particularly during the heating that some reactions are sufficiently fast to meet this criteria
The spontaneous discoloration294dwellings" or "black magic dust" (BMD). airborne contaminant, the reaction rate must be competitive
This phenomenon is known as "black293in triggering the phenomenon. with the rate of building air exchange. They demonstrated an
particular, the type of air flow were shown to be decisive factors for gas-phase chemistry to meaningfully remove
infrared thermography, colder wall areas, thermal bridges, and, in radical generally follows expressed in the formk(T) = Ax the Arrhenius
By means of timeresolvedA 19Figure a heater with clear discoloration. of alkene and NO phase reactions with ozone and the hydroxy
shows the wall aboveB 19Figure responsible for the phenomenon. gas-equation(65T), where B = EB/exp(−∙The temperature dependence
can be concluded that thermophoresis and diffusiophoresis are principally is often be described by the more complicated relationship k(T) = Aa
the pattern of the deposits. On the basis of this and other results, it and can301,302T ∙)asdiscussedearlier.However, thetemperature dependence
image shortly after the start of heating. The flow profile largely matches /R. the reactions of alkanes do not follow a simple Arrhenius law
shows the thermographic295 Note that2T).B/exp(−∙302example, for the reaction of ozone with NO,
includes walking and housekeeping, especially vacuuming. reactions of interest have activation energies that are relatively
is essentially dominated by human activities in the interior. This Table small, and the resulting temperature dependence is weak. For
any data have been published on this, since resuspension Most bimolecular gas-phaseE a kJ/mol (see data in = 12.4B·R = 4
be resuspended as a result of temperature influences. However, hardly radical reactions have negative activation energies (see B values in
the question of the extent to which particles deposited on surfaces can same increase in temperature. Many energy of 6%by only about
There is also296Nazaroff 297through abrasive wear of surfaces. Qian et al. kJ/mol, the reaction of α-pinene and ozone increases 4.4for the
pointed out that such activities may also generate new particles298 (298–308 K). With an activation lead to35°C to 25from 18%by about
in their review article on induced particle resuspension. In principle, ). This means that the rate of reaction will only increase4Table °C
also address the interaction of particles with the surface ), which
( A) ( B)
19F I G U R E after the start of heating(

soiling pattern; (B) Thermographic
image of the wall surface shortly
A) Wall above a heater with distinct293
| 60of 33
4TA B L E K, Arrhenius parameters A and B and the influence of temperature 298of indoor gas-phase reactions, rate coefficients at
Examples
K 298in k for
Reaction k (298 K) (cm3molecule −1s −1) A (cm3molecule −1s −1) B (K) % change→K 308
O3NO +→O 2+ NO 12 1.9·10−14 3.0·10−12 1500 +17.8
O3+ NO 2 →O 2+ NO 13 3.2·10−17 1.2·10−13 2450 +30.6
O3pinene →+ α-products 2 8.4·10−17 5.0·10−16 530 +5.9
O3pinene →+ β-products 2 1.5·10−17 1.2·10−15 1300 +15.2
O3limonene +→products 2 21·10−17 2.95·10−15 783 +8.9
OH + α-pinene→products 2 52.3·10−12 1.21·10−11 −436 −4.6
OH + β-pinene→products 2 74.3·10−12 1.55·10−11 −467 −5.0
OH + limonene→products 2 164·10−12 4.28·10−11 −401 −4.3
1Values taken from Seinfeld and Pandis.301

2Values taken from Atkinson and Arey.302
increases. Further examples of these reactions are shown in and Arey 9.2|Homogenous chemistry
of saturated and unsaturated hydrocarbons with OH, O 4Table
Atkinson .303decreasing reaction rates as the temperature - basedmaterials is of particular importance for the indoor environment.
Arrhenius coefficients valid for certain temperature3,and NO 3ranges. of urea-formaldehyde resins used in themanufactureofwood
have compiled kinetic constants for the reaction and also provide by reaction with water. The subsequent hydrolytic decomposition
K 298at describes the decomposition of a chemical substance
generalization. Molecules known as tropospheric reservoir molecules important reaction taking place in building materials. Hydrolysis
to chemistry, someequilibriaand reactions areanexception to this a liquid, solid, or other condensed phase. Here, we focus on hydrolysis, an
Although many gas-phase reactions are relatively insensitive301 Homogenous chemistry occurs within305This reaction ( 70equations and
include peroxides, dinitrogen pentoxide, and peroxyacetylnitrate 71) is known to be one of the main sources of indoor formaldehyde.
conditions allow for a shift in equilibrium that releases them. Examples

2N − CO − NH2HCHO +⇄H 2N − CO − NH − CH2OH (70)
act to temporarily store reactive molecules and radicals until
2N − CO − NH − CH2OH + H2N − CO − NH2 ⇄H 2N − CO − NH − CH2NH - CO - NH -2+ H 2O (71)
molecules M) to the acetylperoxy radical and nitrogen dioxide. with relevance for the indoor environment. The general reaction
( PAN). PAN decomposes (induced by collisions with surrounding Furthermore, esterhydrolysis isawell-knownandwell-described reaction
equation(72) leads to the formation of alcohols and acids.

H3C(O)OONO2M +⇆CH 3C(O)OO + NO2+ M (69)
1C(O) − O − R −2+ H 2O →R 1COOH + R −2OH − (72)
kJ/mol, 115With an activation energy of about 304order of hours.

a factor of five for an increase of temperature from products occurring indoors is provided by Uhde and Salthammer.
the rate of decomposition is also important. In the atmosphere, the serve as flame retardants. A summary of hydrolytic decomposition
°C. The35°C to 25lifetime against thermal decomposition of PAN is on are used as solvents, acrylates as adhesives, phthalates, and
equilibrium constant for PAN decomposition can increase by nearly adipates are common plasticizers and phosphoric acid esters esters
surface301deposition of reactants and the indoor concentration of NO Acetic acid306
the might expect PAN to approach equilibrium. Note that loss by is by far the fastest reaction under environmental conditions.
order of hours, we resulting PAN concentration. As noted in Section latter reaction also being called saponification. Saponification
Since the timescale2of air exchange in many buildings is also of the place in a neutral medium, acid-catalyzed or in an alkaline medium, the
will also influence the7.5PAN, other peroxides, and N The hydrolytic reaction of esters can take307diethylhexyl acetate. -2or
expect decomposition of some thermally sensitive species, including ethylhexanol from DEHP-2acid from n-butyl acetate and the formation of
complete decomposition 1and the lifetime of PAN is only about butanol and acetic-1by hydrolysis. Known examples are the formation of
min. Therefore, we can that temperature, equilibria favors nearly covering. As a result, ingredients of the covering and adhesive decompose
°C (or more near heat exchanger surfaces). At50ducts can rise to and often retains excessive residual moisture when laying the floor
with continuously operating central heating ,2O5systems. floor structures are regularly observed in the interior. Concrete is alkaline
the temperature in heating and air conditioning season in buildings explains that hydrolytic decomposition reactions in connection with new
during the heating This

|
often formulated as a pseudo first-order law due to the excess of OH effects, but the adipate has two centers of attack for the nucleophile.
of esters follows a secondorder kinetic law, which, however, is by mesomeric stabilization. The acetate and adipate have inductive
Formally, the alkaline decomposition−to the empirical Arrhenius The low reactivity of the phthalate can be explained
temperature dependence of the reaction can be described according The SPARC algorithm calculateskOH °C. DePuy and Mahoney25at
ions. Theequation (65of chemical reactions, based on the transition state. s) for nBAc∙l/(mol 0.075 =312give the value kOH - lifeof
an exact theoretical treatment on the temperature dependence neglecting the reaction in acidic and neutral mediumatpH8ahalf
). The Eyring equation, which is not discussed here, offers6,308 adhesives is about 20s) for nBAc at ∙l/(mol 0.065 =t2/1 = 0.693/(065.0∙10−6
at 10areonly available for a few indoor-relevant esters. Values between Aksnes and Libnau. hydrolysis of ethyl acetate, a common component of
Hydrolytic rate constants−4 10s) and ∙l/(mol−2°C–30°C. 20phthalates alkaline 4°C. When and consumer products, was carried out by
alkaline environment are given for acetates and and Mahoney∙l/(mol months. A study on the temperature-dependent
307,309,310According to Harris,311reaction enthalpies ∆RH s) for the into the ambient315air for months to years. Schwarzenbach et al.
linear-free energy relationships (LFER). 40are above 312state ∆RH = ) s results,which can therefore release their decomposition products
kJ/mol. For n-butyl acetate, DePuy kinetic constants use various in a slightly alkaline environment and the temperature increases by
kJ/mol. Theoretical approaches to calculating 44.4313 precisely: The reaction rate doubles when 10acid esters react only slowly
et al. 20Figure shows the alkaline second-order kinetic constant kOH SPARC K. These data show that carboxylic principle of van't Hoff very
with higher rate constants than the 314to the observations by Wolfe of nBAc. The temperature dependence of the reaction follows the
ethylhexyl esters. This corresponds-2of various esters calculated range measured reaction constant is ∙L/(mol 0.074with SPARC is
and these in turn faster than the phthalates. 35°C to 15range from s), the value calculated∙L/(mol 0.085s). The half-life is thus in the
faster than the acetates310°C. It is obvious that the n-butyl esters have carboxylic20At 40acid esters in neutral, acidic, and basic media.
for the temperature same alcohol group, the adipates hydrolyze °C, the provide a general discussion on the hydrolysis of
With the environments has been described in various works. Björk et al.
mechanism. 21Figure involves the nucleophilic attack of the OH The decomposition of floor structures in damp and alkaline316Wilke et al.
the first reaction step ,−According to a so-called addition–elimination were identified as decomposition products of various esters. A study by
ion, followed by elimination. Therefore, the entire reaction follows pH. Among other compounds, 2-ethylhexanol, isononanol, and isodecanol
of degradation products from different materials depending on the
-1.5 measured the release317acid were found as potential hydrolysis products.
-2.0 particular, 2-ethylhexanol, acetic acid, hexanoic acid, and ethyl hexanoic
DnBA of VOCs and SVOCs from floor structures and their components. In
-2.5
deals with the emission
-3.0
nBAc
SjöbergandRamnäs such as 318 600–500for the high emission rates of
ln kOH (l mol-1s -1)
-3.5 conclude that essentially adhesive components-2butyl acrylate and -1

-4.0 DnBP ethylhexyl acrylate are responsible the FLEC. The authors
-4.5 DEHA in an alkaline environment over a period of several months using

ethlylhexanol from various flooring systems-2and
-5.0 EHAc
µmonitoredtheemissionratesof1-butanol 1000h) (1-butanol) and ∙/(m²
-5.5
h). Chino et al.µg∙g/ (m²319and adhesives. Anderberg andWadsö
-6.0 DEHP
come to similar results when examining PVC floorings320
-6.5 decomposition of floor adhesives using calorimetric measurements.

0.003300.00325 0.00335 0.00340 0.003450.00350 also determined a pH-dependent
T-1( K) room temperature321contribute to the overall degradation rate.
abiotic mechanisms on the degradation of phthalates in dust at
0 2F I G U R E - dependent second-order rate constants
Bope et al. that at high relative humidity biotic and
acetate; and DEHP: di-kOH of various esters in an alkaline environment. The
have shown through experiments
n-butyl phthalate; DEHA: di-kOH ethylhexyl phthalate-2Temperature
ethylhexyl adipate; EHAc: 2-ethylhexyl-2for the hydrolysis hydrolysis reaction is a necessary process for the polymerization
SPARC. DnBA: di-n-butyl adipate; nBAc: n-butyl acetate; DnBP: di- of silicone sealants. From a chemical point of view, the polysiloxanes The
values were calculated using are derived from silica, whereby OH groups are replaced
1 2F I G U R E Alkaline hydrolysis of esters

| 60of 35
2 2F I G U R E be released during the reaction

with water (R = alkyl groups). X
denotes functional groups that can compounds
scheme for the polymerization
process of silicone-based sealing Reaction
groups (X). When reacting with water, these groups are released informative. For ceiling tiles, carpet, and painted drywall, Rim et al.
into the ambient air as amines, acids, oximes, or alcohols (see reacting with a squalene-coated surface, Petrick and Dubowski326
by alkane residues (R) and functional22Figure well studied. indoor-specific investigations and some that are related and ozone
sealants can be strong emission sources for VOCs. The substance measured uncertainty.” In a study of the kinetics and chemistry of
butanone oxime (methyl ethyl ketoxime = MEKO), which is classified °C vs. 22°C, but the differences were “within the28velocities at
-2as a suspected carcinogen and skin sensitizer, has been particularly mainly by its reaction with unsaturated327dependent.
). Especially during curing, silicone322observed emitter of sealants. not anticipated to be very temperature to indoor surfaces, driven
In addition to MEKO, acetic acid is a frequently323 observed slightly increased ozone deposition organic compounds, are
published for many of the chemicals that are relevant indoors, kinetics over a fairly broad temperature58range (24°C, 37°C, and
parameters, reaction enthalpies, and entropies have been °C). In general, ozone deposition rates increase in the oxidation
reaction increaseswith increasing temperature.Arrhenius observed no significant328,329
depend on contribution of hydrolysis products to indoor air pollution. their squalene study, Petrick and Dubowski
general, therateof summary, the kinetics and thermodynamics of hydrolysis of products, from nearly in-volatile to very volatile (e.g., formaldehyde). In
In307,308,324various factors, including pH and steric effects. In with condensed phase unsaturated organics generate a wide range
so that it becomes possible to estimate the Ozone reactions327and reservoirs of volatile decomposition products.
of ozonides and peroxides that serve as low-volatility intermediates
in emission rates may also be due to more rapid thermal decomposition
9.3|Heterogeneous chemistry more rapidly from the surface at higher temperatures. Some increases
observed that reaction products volatilized330–333
a condensed phase such as a surface layer of grime is one prominent In a study of photocatalytic paints, Gandolfo et al. °C; from 334rate of NO
indoor example. The formation of HONO from the reaction of NO the surface for an increase in temperature from 2°C, the NO 40°C to 32
of the gas phase) depositing and reacting at the interface or within the range of 32°C to17observed a threefold increase in the uptake to
are components of two or more phases. Ozone (a component 2°C–32°C.22NO and HONO measurably increased over
reactants increase convective mass transfer to surfaces (see Section 2 did not increase, perhaps suggesting transport limitations. Yields of
and H2Heterogeneous chemistry refers to chemistry in which uptake rate
of temperature on surface boundary layers: weak for mean changes
in temperature, but more strongly when temperature gradients
absorbed. Heterogeneous reactions that are limited by gas-side mass 9.4|Particles of outdoor origin
transfer of reactants are expected to be influenced by the effect
or reactant, but decrease the activity of a primarily gas-phase reactant large changes in thermodynamic conditions. As discussed in Section
by reducing its surface concentration and mean time adsorbed Particles that infiltrate fromoutdoors can experience rapid and7
in temperature may increase chemical activity of a low-volatility higher or lower than outdoor air. Several authors have observed
of heterogeneous chemistry can be complex. An increase modeled indoor/outdoor differences in particle composition °C
to be the case for very reactive gas-phase species like the OH radical,8.2 that is driven at least in part by these temperature gradients. and
O on an indoor surface is another. The temperature dependence 20indoor temperatures can easily be ,335,336Arp et al. 146,147Section
). This is likely325ozone, the nitrate radical and other oxidants. /particle behavior in different regions as a function of temperature
and depending on the surfaces, for and relative humidity and derived pp-LFER descriptors (see also
can start with ozone-surface chemistry, as there have been a few general, during the cool season, particles of outdoor origin may4.3).
temperature-dependent heterogenous chemistry indoors. We gas shed some of their mass simply by the reduction in partitioning In
There have been few studies that explicitly investigated have investigated the dynamics of particles and ambient
|
(A)5 (B)5 3 2F I G U R E Partitioning factor Fi

Hydrocarbon-like organic aerosol Oxidized organic aerosol model results presented in Cummings et al.
4 4 % by Cummings and based on
i
i
Partitioning Factor,F
Partitioning Factor,F
aerosol. Shaded area represents95
3 3 confidence intervals, provided organic

- like organic aerosol and (b) oxidized
temperature differences for (a) hydrocarbon
2 2
of indoor–outdoor observed by Avery et al
for residential340settings as a function
1 1
Red lines represent trends341
0 0
- 20 0 20 40 60 - 20 0 20 40 60
∆T (oC) ∆T (oC)
in-out in-out
underpredict the mass concentration of particles and their components. enough for particles to reach their critical supersaturation point.
removal (e.g., filtration and deposition) of particles can over- or conditions. In indoor environments, the relatively slow rate
cooler than outdoor air. Therefore, models that only consider mechanical exchange should provide enough time for particles to undergo favorable
sources of SVOCs contribute mass as well, especially if indoor air is deliquescence if RH rises above the DRH, or effloresce when dry of air
opposite occurs in warmer months if indoor air is cooler. Indoor efflorescence can be abrupt, occurringwithin seconds of reaching
(i.e., volatilization) that occurs in the warmer indoor environment. The337 – Deliquescence and
340As an example of this effect, Cummings et al.340 suggest that HVAC influences the amount of aerosol liquid
different US climate zones. They report a partitioning factor,16 water, thereby altering partitioning of water-soluble species. outdoors
in the aerosol phase for different indoor concentration of component measurements of the composition of aerosols both indoors and
and other factors for typical aerosols across chemical components and dry (winter), to shift particles away from their anticipated
divided by the concentration of componentFi– outdoor temperatures water content for that indoor environment. Winter/summer hot
, defined as thei predicted the concentration of various removal which air is cold and humid (summer) or water-soluble gases.
only considering mechanical removal processes. We show in These abrupt changes make it possible341,343for HVAC systems, in
than i aerosol phase when considering thermodynamics and mechanical water-soluble species. During the heating season, the duct air is dry
expected 23Figure 0.5in the during the cool season, this ratio can be less and hot, inducing efflorescence or drying of the particles. Because
warm homes organic aerosol can be as much as five times greater than cannot absorb the air indoors is also below the DRH, preventing subsequent
when based on mechanical processes alone. Alternatively, in deliquescence, the particles remain dry and
air is cooler), the indoor concentration of hydrocarbon-like in the HVAC duct during the cooling season (low temperature, high
the temperature gradient is strongly negative (indoor of humidity) induced deliquescence of hygroscopic particles thereby
in this format were generously provided by Bryan Cummings. When ensuring indoor aerosols had sufficient water for partitioning
confidence intervals for residences; results 95%the The authors of that study observed more reduced nitrogen species
associated with third-hand tobacco smoke in summer aerosols
than in winter aerosols. They hypothesized that the conditions
9.5|Deliquescence and efflorescence
is the process of a particle abruptly absorbing water when the 9.6| Formation of secondary organic aerosols
DeliquescenceRH of the solid is equal to that of the saturated solution. ( SOA)
rises above the point at which the Gibbs free energy301This RH for (NH
usually associated with salt particles. For example, the DRH reactive organic gas (ROG) that is converted to aerosol according to Y = ΔC
is known as the deliquescence relative humidity (DRH) is4)2SO4and for NH , The yield Y for the formation of SOA is defined as the mass ratio of aSOA/Δ
80%is 4HSO4, .40%the DRH is 342in mass due to water uptake at a specific CROG.344As shown in 24Figure a broader spectrum of unsaturated organic
For sulfuric acid and purely organic particles, there is no abrupt changeRH vary less, and there is usually no direct sunlight indoors. However, there is
Instead, mass changes smoothly with .RHto overall hygroscopicity. and formation rates will also be different. Temperature and humidity
depends primarily on the salt composition but organics can contribute inside are different from those outside; therefore, the SOA composition
particles composed of a mixture of inorganic salts and organics, the DRH the viscosity, morphology, and hygroscopicity of particles. The conditions
For .342The DRH is generally weakly dependent on temperature, 301low oxidized organics that contribute to particle organic mass and can alter
particle will return to the crystalline/dry state (efflorescence) at also by acid-catalyzed chemistry. The reaction processes generate
only changes by a few % over a typical range of indoor temperatures. The emissions, oxidation of precursors (gas phase and surface bound) and
andRH and for the solution to reach a critical super saturation point. of indoor SOA is a complex multistep process driven by direct VOC
once enough time has elapsed for water to evaporate the formation ,
| 60of 37
in 4 2F I G U R E the indoor environment

of secondary organic aerosols (SOA)
Formation mechanisms
grow grow
coagulation
condensation nucleation
evaporation evaporation
gas phase molecules
reaction (O3OH, NO ,xacids, etc…) ,
emission precursor VOCs (in gas phase or on surface)

source
solid primary particle
the higher indoor concentrations of influential precursor molecules. temperature. Moreover, Youssefi and Waring352be taken into account.
researchers have observed a higher yield of SOA at indoor environment, for example the use of terpene-rich products, must
compounds at higher concentrations. Many345 yields are highly variable indoors and that the special conditions of the
treatment of SOA formation and evolution in ambient air. literature and own theoretical considerations. It was found that the SOA
gases to the particle. Seinfeld andPandis provide a comprehensive evaluation of the SOA formation indoors using data from the
at primary particles and also involves partitioning of other low-volatility carried out a comprehensive
can be homogenous via nucleation or heterogenous via condensation
Secondary organic aerosols formation301conditions, Leungsakul et al.
rates but also increases the volatility of SOA components. Under ambient 9.7|from building and consumer products
An increase of temperature generally increases reaction346by Odum et al. Temperature-dependent emissions
with decreasing temperature. This is in agreement with previous results
that aerosol yields from the limonene/ozone reaction tended to be lower been examined in detail for many years. chemical components (see
found344K, Sarwar and Corsi 300and 280the temperature range between temperature-dependent emission products. 129behavior of products has
absorption model. Based on results of indoor-related SOA studies in This relates to both the5Table ) and sensory perception.353The
aerosol mass concentration and the temperature-dependent gas/particle - based materials, in vulcanization processes and in many recycling
describing SOA formation as a function of the organic347III et al. during manufacture. This is a wellknown effect in wood
is compensated by the increasing gas/particle partitioning. Cocker that are converted into new substances at elevated temperatures
the decreasing terpene/ozone reaction rate with decreasing temperature porosity of the respective material. In addition, various temperature
conclude that348the presence of aqueous seed aerosols. Saathoff et al. effects must be considered. Many materials contain ingredients
and found a dependence of the SOA yield on the relative humidity and and in the gas phase can be reliably calculated using the known kinetic
studied the α-pinene/ozone system349at room temperature. Waring et al. laws, diffusion in solids depends on the chemical composition
addition, limonene was found to produce more SOA than α-pinene general laws for solid products. While the dynamics of molecules
on organic aerosol mass concentration and inversely on temperature. In It turned out that it is difficult to derive306
K. It could be confirmed that SOA yields depend 313and 243between phase of solid products are the most difficult to describe theoretically.
of SOA by ozonolysis of α-pinene and limonene in the temperature range emission behavior. The temperature-dependent emissions during the use
studied the formation350and mass formation; the presence of NO and NO vapor pressure of the released compounds, which has an influence on the
the water vapor concentration decreases both the SOA number accelerate the drying process and at the same time increase the
SOA formed due to an increase in gas-to-particle partitioning; increasing application are usually controlled by evaporation. Higher temperatures
to increase the number of nucleated particles as well as the mass of Emissions during the drying process of liquid coating materials after25
data, concluded the following: Decreasing temperatures are expected Figuresubstance reaches the surface by source-phase mass transfer (
examined the formation of SOA in indoor spaces and, based on literature used in a material or is formed by a reaction from a precursor. The
have2 shows the different steps of the release. A substance (target compound) is
km the next step, the substance passes through the boundary layer (
the mass of formed particles. Taking all factors into account, Waring depends on the concentration difference between material and surface. In
ozonolysis; background particles could increase amount with increasing is the mass-transfer coefficient), whose ratekgat the material surface
that the rate of indoor SOA formation is reduced by a small351from terpenoid ). This gas-phase mass transfer depends on the concentration difference
reduces themagnitude of SOA formation predicted

|
5TA B L E during application or use

Material Compounds References (chronologically)
to the influence of temperature
Chipboard Formaldehyde Andersen et al. (1975)394 during production and processing, others
UF-bonded boards Formaldehyde Myers (1985)395 relate to the influence of temperature

organic compounds from building
Variety of indoor materials VOCs Tichenor (1989)396
products. Please note: some studies of volatile
Particleboard Formaldehyde Wiglusz et al. (1990)397 temperature dependence of the emissions
Dry cleaned fabrics Perchloroethylene Guo et al. (1990)373 Publications on the
Floor wax VOCs Chang and Guo (1992)398
Textile floor coverings VOCs Sollinger et al. (1994)374
Building materials VOCs Wolkoff (1998)399
Paint and varnish VOCs Haghighat and De Bellis

(1998)12
Laminate flooring Formaldehyde and VOCs Wiglusz et al. (2002)400
PUR-adhesives Diisocyanates Wirts and Salthammer

(2002)360
PUR-adhesives Diisocyanates Wirts et al. (2003)361
Oriented strand board VOCs Makowski et al. (2006)363,364
Dry building materials Formaldehyde Zhang et al. (2007)376
Porous building materials Formaldehyde Deng et al. (2009)388
Different wood species VOCs Hyttinen et al. (2010)367
Building materials Formaldehyde Xiong and Zhang (2010)15
Wood-based materials Formaldehyde Xiong et al. (2011)371
PVC flooring DEHP Clausen et al. (2012)14
Particleboard Formaldehyde Frihart et al. (2012)401
Building materials Formaldehyde and VOCs Xiong et al. (2013)375
Reference material Formaldehyde Wei et al. (2013)392
Reference material Toluene Liu et al. (2014)391
Vinyl flooring, mattresses Phthalates and Liang and Xu (2014)383

alternatives
Latex paint Phthalates Schripp et al. (2014)358
Wood-based materials Aldehydes Suzuki et al. (2014)368
Building materials Formaldehyde Huang et al. (2015)378
Medium density fiberboard Formaldehyde Liang et al. (2016)377
Reference material Formaldehyde Salthammer et al. (2017)
Building materials VOCs Huang et al.(2017)381
Polyisocyanurate foam Organophosphate esters Liang et al. (2019)384
Polyurethane mattresses VOCs Oz et al. (2019)385
Building materials Formaldehyde Zhou et al. (2019)386
Building materials VOC Huang and Joillet (2019)382
Wooden furniture VOCs Wang et al. (2021)387
Building materials VOCs Piasecki et al. (2021)389
(Csurface) and in the air (Cair). For kg >>k m,the drying/curing phase. For test methods. This subject will be dealt with separately in a later section.
applies to most wet-applied or liquid products during indoors from the results of simple
also depends on the thickness of the boundary layer, dominates. This

the gas-phase diffusion, whichkg <<k m,transfer inside the material.
the emission is controlled by mass354 Liquid products |9.7.1
used by companies to estimate the formaldehyde concentration
the emission under different climatic conditions. Such models are studies were carried out on various types (see ). Chang and Guo
materials. Empirical models have been developed to predict With regard to the liquid products intended5Table for curing, emission
A special case arises for the release of formaldehyde fromwoodbased 355examined the formation of aldehydes in alkyd paint and
| 60of 39
was investigated as a function of temperature.360,361band.

indoor air
of viscosity measurements and monitoring of the IR polyurethane
evaporation-controlled kinetics to solid-phase diffusion MDI and
Cair kinetics could be precisely characterized on the basis from
transition volatilization enthalpies were in the range of 4,4- controlled
boundary layer -2,4For36190 kJ/mol. –80′-MDI (methylene diphenyl diisocyanate), the
kg
followed the Clausius–Clapeyron law. The experimentally determined
Csurface
- MDI, and HDI (hexamethylene diisocyanate), the emission rate
solid material(source) msurface MDI, 4,4′-2,4For 360
km
Solid products |9.7.2

mmaterial
target compound accessory components such as fats, acids, and terpenes.
consists of different proportions of celluloses, hemicelluloses, lignin, and

reaction
the manufacture of wood-based materials. Depending on the type, wood

other reactants
The effects of temperature are particularly evident in362
aldehydes decrease with increasing temperatures of hot pressing.
precursor
found that the emissions of terpenes, saturated and unsaturated aliphatic
of oriented strand board (OSB) from scots pine, Makowski and Ohlmeyer
5 2F I G U R E solid material via a boundary layer into indoor air. During the production363the terpene emissions were largely unaffected.
Scheme for the release of chemical substances from a homogenous °C, while170aldehyde emissions than boards whose chips were dried at
Cair and Csurface refer to concentrations in the gas phase, mmaterial °C showed lower120conditions, OSB boards whose chips were dried at
andmsurface refer to concentrations in the source phase must be dried before the OSB is manufactured. Under identical pressing
The strands364are released from hemicelluloses under thermal stress.
be controlled by a consecutive first-order reaction mechanism. Although such as acetaldehyde, formic acid, acetic acid, and furfural
et al. the experiments were carried out at constant temperature, it can a higher mobility of the ingredients, but by chemical reaction. Compounds
assumed that the reaction constants obey Arrhenius’ law. Guo - dependent emissions of certain compounds are often not caused by
are vapor pressure, diffusivity and amount356applied. Chang et al. In general, with wood-based materials, temperature365,366Hyttinen et al.
found that the autoxidation process was of individual compounds 367wood. In their investigations on wood-based materials, Suzuki et al.
state that the three parameters required to predict emissions et al. emissions of acetic acid and furfural in heat-treated wood than in air-dried
investigated the release of VOCs from petroleum-based paint357and measured significantly higher368with increasing temperature.
found a double exponential decay law. The fast component found higher emissions of acetaldehyde
in the initial phase was related to the evaporationcontrolled paint and

drying process, followed by a slow component, representing 10·7on the porosity of the material, are in the range of
the solid-phase diffusion-controlled process. Schripp room temperature, the diffusion coefficients of typical VOCs, depending
successfully used in a study on dermal exposure to DEP358and DnBP. For solid products and−9 10∙1m²/s (wallpaper with paste) to −6board).
characterized the formaldehyde emission from a latex rate that was m²/s (gypsum267,370Xiong et al. 371 10·9diffusion coefficients between
pressure. The emission parameters determined with the help determined−12 10·3m²/s and −10in wood-based materials. Xu and Little
the boundary layer theory could be accurately reproduced. This vapor m²/s for formaldehyde372 10·1estimated a diffusion coefficient of −13et al.
allowed the paint to be designed to have a target emission of from the slope of the straight line vary from product to product. Guo
test chambers. The increase in steady-state concentration at higher the emission rate in a test chamber. The respective enthalpies that result
temperature in the chamber correlated roughly with the higher temperature and the logarithm of the steady-state concentration or
phthalate (DEP) and di-n-butyl phthalate (DnBP) from latex paint in most cases a linear relationship is found between the reciprocal absolute
investigated the influence of temperature on the release of diethyl359 parameters, and the emission rate. It is no surprise that in
effects. discussed by the authors that partition coefficients are dependent relationships between the ambient temperature, other thermodynamic
on temperature and that higher temperatures reduce sink in PVC at room temperature. Attempts are often made to derive general
However, it is also m²/s for DEHP373perchloroethylene in the cleaned textile. Sollinger et al.
contain various diisocyanates as components, the curing process relationship between temperature and the mean retention time of
of paints, which dry physically, the curing process takes place here in various types of dry cleaned fabrics and established an empirical
through a polymerization reaction. For adhesives and resins that have determined adsorption enthalpies for perchloroethylene374in static
to temperature effects during curing. In contrast to many types have investigated the volatilization enthalpies of various VOCs on carpets
Isocyanate-containing products are particularly sensitive

|
material377and a certain type of adhesive. In later work, Huang et al.

Air in Air out et al. respect, the measurement result can only apply to a certain
also be noted here that temperature effects on formaldehyde
y(t) from woodbased materials are usually caused by chemical should
V( volume) reactions and not by physical effects such as diffusion. In this emissions
to determine the release of formaldehyde from MDF. However, it
setup the socalled C-history method. 378determine the parameters
C(x=L,t) =Kma·y0( t) hm dynamic experiments usingDm,K ma, and C0used a similar experimental
A( surface)
X=L were able to directly from MDF in temperature-dependent
for the release of formaldehyde379
Dm x release rate of DEHP from PVC was investigated by Clausen et al.
C0 C(x,t) The temperature-dependent14concentration) and the parameter
- dependent vapor pressure of DEHP (expressed as saturation
X=0
relationship between the temperature a critical analysis by Liu et al.,
be established. However, iny0- Emission-Cell (FLEC). A linear
26F I G U R E Schematic representation of VOC emission from
convective mass transfer. The figure was adapted from Liu et al. (2013). with the Field-and-Laboratory to the vinyl flooring surface, could
a homogenous solid material including369D m - phase diffusion coefficient, that is, the DEHP concentration immediately adjacent ,369
is the materialC0is the initial material-phase compound concentration, C(x other substances. The comparison of the methods for determining
t) is the material-phase compound concentration at position x and time t,
it was stated that this relationship does probably not exist forDm,K ma
air, y0(t) , compound concentration in the air adjacent to the material surface
material ,y0surface, and sink effects must also be taken into account.
coefficient. See Liu et al.K ma partition coefficient between the material and
is they(t) is the gas-phase concentration, and hm is the gas-phase and weeks, the emission rate depends on the air velocity at the
is the convective mass transfer369for more details and related models of the SVOC DEHP takes place over many in a chamber takes less than
is a typical VVOC, equilibrium 20contrast, the equilibrium
h, and sink effects are negligible. In a fundamental problem. Formaldehyde
of vaporization of the respective compound. within a plausible range of for formaldehyde and DEHP illustrates380
70 kJ/mol, but there was no correlation–22with the enthalpy Huang et al.381property–property relationship (QPPR) shown in
chamber tests. The values determined were developed the quantitativeequation (73temperature (
of emission rates refers to themodel originallydevelopedbyCox et al. predict diffusion coefficients for a wide range of organic chemicals
Most of the work on the temperature dependence13was later expanded and materials as a function of the molecular weight (MW), absolute
for polyvinyl chloride (PVC), which369and also used for other materials. 375 for T), and the material-specific coefficients b material types.
26Figureadvanced model for SVOC emissions is discussed by Xu and Little. consolidated 32chemicals in 158) to measured diffusion coefficients
is no interaction with the chamber walls or with airborne particles. An 1103and τ. They used a training dataset of
a material. It is assumed that the material is homogeneous and that there
−3486
the test chamber concentration of a certain compound after release from ogDm− =2.49−6.39∙logMW+b (73)
T
shows a simple scheme for determining372Zhang et al. 376shown in
explain that for the scenario 26Figure the diffusion coefficient, ,Dm In a later study, Huang and Joillet382relationship (QSPR) to predict
the partition coefficient, ,Kmaand the initial concentration ,C0and that developed a quantitative structure–propertyKma measured 991dataset of
are the three key parameters used to predict the VOC emissions for a number of chemical-material combinations. The authors compiled aK
of the target compoundDm andK ma temperature-dependent values for mamaterial types. The multiple linear regression model shown as
and theoretical approaches, these authors were able to determine consolidated 22chemicals in 179values for equation (74) predicts Kma
be strongly affected by temperature. Using a combination of experiments as a function of the chemical's octanol/air partition coefficientKOA
mayKma and Dm from four different materials. In later work, Xiong et al. the enthalpy of vaporization (Δ ,vapH), the
for the release of formaldehyde375experiments, Xiong and Zhang absolute temperature, and a material-specific coefficientb.
material and the target compound. In sophisticated static chamber ( )

ogKma = −0.63+0.38∙logKOA +0.96∙
ΔmaH ∙ − 1 1
+b
be well described with semi-empirical models, but only for the respective 2.303∙R T 298.15
in different building materials. The experimental observations could again (74)
between the emission rate and temperature for chemical pollutants
examined the association15increases significantly with temperature. Liang ΔmaH 1.37 Δ =vapH of the partitioning between material and air. –
measured formaldehyde content of the material and that the release rate in J/mol) is the enthalpy( 14.0
the amount that can be released at room temperature is well below the compounds have been published for a number of other materials.
of formaldehyde from medium-density fiberboard (MDF) and found that - dependent determination of the emission rate of volatile organic
determined the temperature-dependent release Similar studies on the temperature383–388behavior for the individual
All results and models can satisfactorily describe the emission

| 60of 41
replace experimental investigations in the near future. Piasecki et al. product. described in the literature. However, the effect is mostly achieved by
possible to derive of all the publications discussed can be found in incorporating the scavengers directly into the respective
model that can work also has in common that it has not yet been reduction in the release of VVOCs and VOCs from construction
models. A summary389a general, substance and material-independent products by sorptive materials or reactive substances is well The
case. However, all to predict the emissions with the usual emission 410,411
°C was observed. However, it was not possible33°C to 23from correlated with the temperature and materials generally become
3) after the temperature was increased–2by a factor of al. more permeable at a higher temperature, the emission-reducing
of multilayer building materials for floor heating systems with a focus effect decreases with increasing temperature. Wang et
on primers, waterproofing products, and adhesives for wood and of a substance in a layer is positively discussed in Sections
ceramic floors. A significant increase in total VOC emissions (often with increasing temperature (23°C 9.7.2and 8.1the diffusion coefficient
example investigated the temperaturedependent emission behavior dependence of emission barriers, the arguments and various VOCs
for5Table. With regard387apply to the diffusive types. Since to the temperature
chambers and to validate analytical methods. Howard-Reed et al. and found a significant increase in diffusion for formaldehyde
materials have been developed for the purpose to characterize test were coated with a varnish made of polyurethane vice versa.
- dependent emission behavior of a specific product. Reference examined wooden and wood-based furniture, whose→surfaces
can be helpful and necessary to precisely determine the temperature on a chemical reaction, the temperature effect depends on whether
temperaturedependent emission390behavior was investigated by Liu et al. the reaction is exothermic or endothermic. In general, in equilibrium
In some cases, however, it films are loaded with toluene; the step and reactions, an increase in temperature leads to the equilibrium
developed a reference source in which polymer391 shifting in the direction of the endothermic reaction
decayed over time. The formaldehyde source described by Wei et al. °C). In the case of barriers based35
However, it was only possible to set a concentration profile that392
h. The design developed by Salthammer et al. 24over at least
temperature-dependent setting of constant formaldehyde concentrations 9.8|release from wood-based materials

a thin polydimethylsiloxane (PDMS) film cover. This principle enables the Empirical modeling of the formaldehyde
that holds a formaldehyde/water solution with
consists of a polytetrafluoroethene (PTFE) tube393and relative humidity. air humidity. The first empirical model was developed by Andersen et al.
h, and the emission rate could also be precisely set via temperature24 of formaldehyde into the interior depending on the temperature and
compound. This type also showed constant emissions over at least s made it necessary to be able to describe the subsequent release1970
source using paraformaldehyde as formaldehyde-releasing polymeric The increasing use of particleboard for building purposes in the394et al.
is based on a permeation controlled with increasing air exchange. In their original publication, Andersen
can be for decorative reasons or with the intention later Godish decrease in the chamber steady-state concentration
certain surface or product properties. Hanetho are coated. This steady-state concentration to temperature and air humidity; (b) hyperbolic
In many cases, the surfaces of construction products402of achieving in climatic chamber measurements: (a) proportionality of the chamber
and403the release of formaldehyde from wood-based materials. on the basis of the following observations394their model as shown in
discussed that suitable materials can significantly reduce presentequation (76).
discuss the causal mechanisms and temperature dependencies.

(R ∙T +S ) ∙ (a ∙H +b )
with the so-called “barrier effect” of surface coatings. Mostly, it = mgHCHOm−3air (76)
1+ (n ∙c ∕ )
is purely empirical work that describes the effect but does not deal
barrier effect for formaldehyde often404–409of the coating.
water vapor transmission coefficient mechanisms. For example, the R,S ,a ,b , and c are constants depending on the board under con-
Various studies have been published that correlates roughly with the sideration,T is the temperature in °C, H is the humidity in H2O kg−1,n in h
that the diffusion coefficient plays the crucial role. This assumption is the air exchange rate−1volume and the free area of boards in the room.
is certainly plausible as long as the substances are nonreactive. In and α is the ratio between the room ,
the case of reactive compounds, however, there may be other that can be used to describe the release of formaldehyde
demonstrated for the release366of formic acid from particleboard. from wood-based materials under variable conditions of developed
Mechanistic studies assume carbonate can act as a buffer. This was model is accordingly designed for this concentration between
to equations (70) and (71). In stronger than carbonic acid ( empirical and semi-empirical models have been mg/m³. The
substances like calcium of the reverse reaction according 0.62mg/m³ with an average value of 2.24mg/m³ and 0.08range. Other
The reason is a prevention366With a pKa the case of organic acids, alkaline chemical properties of wood-based materials at that 25time. Studies in
formic acid is significantly ,3.8of pKa(1)can proceed according to houses measured formaldehyde concentrations is based on the
so that the exothermic reaction ,)6.5equation (75). The general disadvantage of empirical models is their dependence
on observations. This means that the respective model is usually
aCO3HCOOH 2 +→Ca(HCOO) 2+ H 2CO3 (75)
optimized for the underlying data horizon. The Andersen model
|
temperature, humidity, air exchange, and loading.412–415Salthammer et al. is in principle Meyer et al.(394is also striking that all points for
416a critical discussion of available models. The approach by Berge et al. uncertainties. It of an empirical equation for all types of particleboard
offer417is applied in the ‘Formaldehyde Indoor Air Model by Andersen et al. not possible at all or is at least fraught with great
– Pressed Wood Products’ of the US EPA. for the relationship red) are above the T = 50%°C and 23RH recognized
Meyer at al.418), loading (0.5–2 m²/m³), and air change (0.5–2 h air humidity used by model, which is due to the exponential function
with modified the classic Andersen model. For this purpose, a total of clear that the derivation between chamber concentration and relative
(25–65% chamber tests were carried out on six different particle boards curve. This region is thus overestimated by the 1:1It makes
212variation of temperature (20–28°C), relative air humidity light red and dark418to Arrhenius, as also described by Berge et al.
empirical concentrations ranged from −1basis, which resulted in assumed. However, an exponential relationship analogous products.
and all data, the Andersen model was recalculated on an On the contrary, a linear relationship with temperature417is
on the relative humiditywas 0.6to 0.01have experimentally examined appears to be more realistic. In conclusion, empirical approaches can
data. Themeasured chamber the chamber steady-state concentration the only roughly model the temperature dependence of formaldehyde
ppm. Taking into account determined based on five experimental concentrations in chambers and indoor environments. Due to
). An exponential dependence ofequation (77). large uncertainties, they cannot replace measurements, especially
in case of health-related evaluations of building and construction
( ) 1
= 0.0366 ∙C ref ∙ (T − 13.15) ∙e 0.0403∙RH +2.073 ∙
1+ 2.07 ∙AER
L
(77) 9.9| Temperature-dependent air concentrations
27Figure shows the measured vs. calculated (77equation 717-1 concentrations of air pollutants were examined in a series of studies.
DIN EN loading were varied within the abovementioned limits. The steady Seasonally different196,420–422are therefore not necessarily to be expected.
- state concentrations under standard conditions according to than in summer. Simple correlations with individual climatic parameters
A (circles) and B (squares). Temperature, humidity, air exchange, and the same time, the natural air exchange rates are lower in winter
m³ chamber concentrations for two different particle boards 1- state temperature is negatively correlated with the relative humidity. At
) steady419at T h = 1AER = ,45%°C, RH = 23−1,L m²/m³ were =1Cref with temperature was observed. As a rule, in the colder months, the
ppmfor sampleAand0.039 =Cref ppm for sample B. 0.042 = In very few cases, a simple correlation
Poppendieck et al.247to the building envelope temperature.

It is obvious from 27Figure and production conditions, as already and VOC concentrations at nearly constant indoor period of
for sampleB (squares). This observation is typical for different recipes air exchange rate. The relationship of increasing /outdoor VVOC
that the points for sample A (circles) scattermore than the points concentrations with increasing outdoor temperature temperature and
suggests that emissions of these compounds were related aldehyde
0.16 months. They observed seasonal variations in the indoor15

in a net-zero energy residence located in Gaithersburg, MD over a
0.14
studied the air quality
trailers, the U.S. Center for Disease Control and prevention (CDC)519
0.12
HCHO calculated (ppm)
In investigations on423could be identified as the cause of the emissions.

0.10 material investigations, wood-based materials containing formaldehyde
temperatures were associated with higher humidity. Through additional

0.08
in the warm, humid climate of Louisiana and Mississippi, so that higher
0.06 formaldehyde concentration and temperature. However, this was a study
found a positive correlation between424

0.04
in California, during eight weeks in summer and five in winter. Over
0.02 VOCs were monitored continuously in a single-family house200
425were attributed to the decomposition of wood building materials.
0.00
0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.16 ketones, increased23mg/h at 45°C to 16mg/h at 22from
HCHO measured (ppm) °C. Much of the emissions oxygenated VOCs, including acids, aldehydes, and
- dependent emissions). The sum of emission rates of selected

state 7 2F I G U R E A (circles) and B (squares) as described by Meyer et al. for the background concentration (excluding activity and occupant
m³ chamber concentrations for two particle boards 1steady- temperature-dependent emissions across most VOCs responsible
Measured vs. calculated formaldehyde418indicate chamber conditions of
The investigators observed strong
The red symbols RH = T green symbols represent data obtained with other =
dependency of pollutants in indoor air was carried out by Huangfu et al.
loading rates (L). The in the chamber. The blue solid line presents the 50%
°C and23T relationship 1:1at different air exchange rates (AER) and A detailed study of the temperature426of formaldehyde, acetaldehyde, methanol, and
and RH values For this purpose, the concentrations

| 60of 43
ppb (28 23the indoor air formaldehyde concentration from approximately 21.0 30
experiment started
days period, there was also a steady increase in 7°C over a 24 20.5 28
°C to approximately18.5daily indoor air temperature from approximately
26
air exchange. However, with a continuous increase in the maximum
Room temperature (°C)

24
parameters, in particular indoor temperature, outdoor temperature, and 8
DiBA (µg/m³)
22
warm period
found that the concentrations of the target substances depend on various
6
days with high time resolution. For normal climatic day/night cycles, it was 20
cold period
were measured in four houses in summer and winter over several
4 18
ppb (58 µbenzene 48was clearly linear.µg/m³) to approximately
16
correlation between formaldehyde and the indoor air temperature 2
14
g/m³); the
can be expected for this group of substances. Indeed, Lyng et al. 0 12

0 50 100 150 200
that a clear dependence of the emission rate on the temperature
Day
biphenyls (PCBs) from products is often controlled by evaporation, so
The release of polychlorinated427the study by MacIntosh et al.,

28F I G U R E Concentration of diisobutyl adipate (DiBA) ( )
be calculated from the straight line gradients in good approximation. In and maximum daily room temperature ( ) in a test house in
for various PCB congeners. The respective enthalpies of evaporation could from Uhde et al cold period was February .2018 ,31 –25was May
and the reciprocal temperature according to Clausius-Clapeyron and the warm period ,2018 ,04March – 19The figure was adopted
days. The 184Braunschweig, Germany, over 431
linear relationship between the logarithm of the indoor air concentration
found a428Danish homes, Andersen et al. 73surface wipes in
PCB concentrations over time. In their study on PCBs in air, dust, and the absorption of so difficult. 434the substance from the air into the dust.
of the variability in indoor 79%to indoor temperature, which explained dynamic equilibrium. the substance is solved. This can certainly apply to
PCB levels in indoor air were also linked429 The dust is assumed to be an organic reservoir in which435the
the PCB concentrations were varying, partly due to indoor temperature. there is still no standardized sampling, sieving and measurement
found that in exposed homes technology and the health-related assessment of the result is
to phthalate430exposure in specific types of work environment. in a polymer matrix can accumulate from floors through abrasion
Pilka et al. increasing indoor and outdoor temperature is related why in the dust. Dust is a very heterogeneous matrix. The complexity
metabolites collected during the summer and conclude that with regard to the composition of house dust is one reason
significantly higher urinary concentrations of all monitored phthalate this can also be present in bound form. Plasticizers embedded
concentration in an occupationally exposed group. They observed studies on gas/dust partitioning have been published so far.
was published by Uhde et al. days with a constant air exchange of the contrary, a house dust analysis does not allow any conclusions
and winter season to examine solely on the temperature effect On436to be drawn about the possible release of a substance, since
variation and phthalate collected urine samples in summer and the long test duration, just a few temperature-dependent
over a period of431h 0.3the association between temperature Due to the experimental uncertainties
184A study that focused of various SVOCs in a test house were examined of a substance is dominated by absorption gas phase is given by
The concentrations−1. 28Figure - controlled processes. Bi et al. phase of the dust, the distribution coefficient that the absorption
profile of the room. The source was house dust doped with DiBA. The Under equilibrium conditions and providedKDA in the organic
effects of the cold and hot periods are clearly visible. Similar effects between dust andequation (78).72
were found for other SVOCs, and the results suggest evaporation
Xdust = fom_dust ∙K OA
adipate (DiBA) and the temperature in temperature from DA= (78)
Cg dust
shows the concentration432°C. 30°C to 21profile for diisobutyl
found that the steady 3- state concentration levels increased by a factor of
with an increase of BBzP and DEHP a in test house and et al. Xdust is the fraction of the target compound in dust, fom_dust dust, and
investigated the influence of temperature on the transport is the volume fraction of organic matter associated with between ρdust Shoeib
is the density of the dust. An analogous equation was used by437
K of deuterium-labeled SVOCs from products into dust, a correlation

Gas/house dust distribution |9.9.1 in their study on perfluorinated sulfonamides. In studies of the transfer
DAand KOA was found, but the values scattered widely.438,439

the settled house dust is even more complicated SVOCs with log various reasons for this: Sampling before equilibriumhasbeenestablished,
than between the gas phase and airborne particles. the gas phase and expected dust concentrations were found in some cases. There may be
The distribution of a chemical substance between433to describe In earlier investigations, significant deviations from the theoretically435
This is, for example, due to the fact that forKOA to months to reach variations in the organic content of the dust, an insufficiently knownKOA
or higher sorption from the air into the dust can take days 10of value or underpredicting the
|
-surface air concentration, by Algrim et al. 6Table are shown ΔH

the partitioning behavior. In rates are directly proportional to the near
for partitioning, assuming emissiony0. For SVOCs, ΔH assessing
the results of experiments decrease by approximately a factor of –15of
over a temperature range 1535°C. Not shown in this table are
Source
SER KPA
coefficient will pressure via the ideal gas law, the Algrim et al. 100
increases with T decreases with T
coefficient, via the effective274kJ/mol. Therefore, the material-air partition
is related to the vapor depth is indirectly related to the partition
decreases with T
Resuspe sion
clusters are around diffusivity. Since the saturation concentration
Deposition
KDA
found that the logarithm of the penetration depth was proportional

to the logarithm of the saturation concentration. The penetration
chemical classes. -1uptake of ketones, carboxylic acids, n-alkanes, and
They measured the dynamic274alcohols and for wide range of
the temperature dependence of vapor pressure can may be used
Dust
to estimate the temperature dependence of partition coefficients
experimental evidence with an indoor-relevant material that
29F I G U R E Temperature dependence of parameters for study, therefore, provides unique and comprehensive
of a chemical substance ( indoor compartments ) in different
determining the distribution
10|AND EXPOSURE TO INDOOR POLLUTANTS

extent to which the SVOCs are associated with particles.437 .100% TEMPER ATURE
72and almost al. 1%content of the dust can vary between less than
In particular, the organic440 20%The often used average value of which contaminant is considered (VOCs vs. SVOCs, particle size, etc.).
has been critically discussed by Schripp et79 with some exceptions. Temperature gradients of several
KDA is linked to the temperature via the KOA by the temperature (see induce convection and promote thermophoresis. These or chemistry
value. However, other parameters are also influenced29Figure al., are generalities, that may be more or less dependent on degrees
is of a complex nature. In a reanalysisof adatasetbyFrommeet are also more temperaturedependent than is gas-phase diffusivity
descriptionof the distributionof substances in the various compartments extension, effective diffusivity and condensed phase chemistry
), so that the temperature-dependent441Weschler et al. 124et al. include vapor pressure, partitioning, and fugacity/activity. By
in air, particles, and dust can be determined for phthalates. Parnis range. Phenomena that are most strongly influenced by temperature
showed that only very rough relationships between the concentrations442 °C–34°C30°C–4°C and occupant surfaces are typically in the 1by
used COSMO-RS solvation theory443volatile SVOCs, reported values of extremes, surface temperatures differ from air temperatures
K, with a good agreement for the more volatile SVOCs. For less 298dust at °C. Again, excluding23°C to 18a central tendency around
to calculate SVOC partitioning between air and indoorKDA °C (excluding extremes) with35°C to 15vary from about
this effect to a kinetic delay in which equilibrium after several months. What we have learned so far is that, worldwide, indoor temperatures
is in agreement with the results of Uhde et al., authors attributed exposure to contaminants by the aerosol-to-lung pathway. The influence
achieved for various SVOCs in a test house even431is not achieved. This temperature on other exposure pathways may not be so obvious. We
are significantly lower than predicted. The air and dust was not highlight just a few examples here that may deserve more attention. of
according to which an equilibrium between in inhalation exposure. The observations (and modeling) that show how
The temperature dependence ofKDA was examined by Bi et al.432 particle composition changes as a function of temperature also reveal
house study for BBzP and DEHP. The following values were calculated: how indoor–outdoor temperature differences can influence inhalation
in a testKDA m³/g, 962(BBzP, 21°C) = KDA m³/g,202(BBzP, 30°C) = K DA should be clear to the reader that if an increase in the building average
m³/g, and1970(DEHP, 21°C) = KDA m³/g. Pei et al.258(DEHP, 30°C) = 444of temperature results in an increase in the average air concentration It
have also investigated the temperature dependenceKDA of a contaminant, this will result in a roughly proportional increase
for phthalates and found a linear relationship between logKDA DEHP, the pressures, fugacities, partitioning, reaction rates, and can reasonably span
T. For/1and KDA were in the same order of magnitude as those of Bi et a1. -transfer rates can increase or decrease by factors of <2 to >10. that range, vapor
values432In addition, DnBP and DiBP were examined. °C regionally, seasonally, or even spatially; over20mass
as a whole, personal exposure to many contaminants indoors appears
to be somewhat to very temperature sensitive. Indoor temperatures

Gas/furnishings/textile distributions |9.9.2 Taken
surface temperatures may easily be different by several degrees. For
temperature-dependent emission rate measurements are primarily compartments, microenvironments, and surfaces influence exposure? Indoor
Since emission rates of SVOCs are generally gas-side limited, most How do temperature gradients among indoor
| 60of 45
6TA B L E of phase change, for specific chemicals and chemical classes, derived from primarily from indoor material emission rates
Enthalpy
Chemical Source material T°C)( Parameter ΔHkJ/mol)( References
Organophosphate flame retardants Wall papers 40,25,60 Emission rate 35.1 Ni et al. (2007)445
Pentachlorophenol Treated wood 23,10,30 Emission rate 90.2 Marchal et al. (1998)446
Organophosphate flame retardants; circuit board 60,23 Emission rate 93.1 Kemmlein et al. (2003)447
brominated flame retardants
hexanol-1Ethyl--2 PVC flooring 40,28 Emission rate 107.4 Katsumata et al. (2008)448
PVC Wallpaper 40,28 Emission rate 87.0 Katsumata et al. (2008)448
Carpet 40,28 Emission rate 75.9 Katsumata et al. (2008)448
DEHP Insulator 40,28 Emission rate 109.4 Katsumata et al. (2008)448
Curtains 40,28 Emission rate 50.0 Katsumata et al. (2008)448
BHT PVC flooring 40,28 Emission rate 157.7 Katsumata et al. (2008)448
Phenol PVC flooring 40,28 Emission rate 84.8 Katsumata et al. (2008)448
PVC Wallpaper 40,28 Emission rate 81.9 Katsumata et al. (2008)448
DEHP Pure DEHP 35.4,23, 47.4, Vapor 95 Clausen et al. (2012)14

61.1,55.3 pressure
DEHP PVC Flooring 35,23, 47,55 Emission rate 99.3 Liang and Xu (2014)383
DINCH Mattress Cover 35,23, 47,55 Emission rate 70.9 Liang and Xu (2014)383
BBP PVC Flooring 35,23, 47,55 Emission rate 56.4 Liang and Xu (2014)383
DEHA Mattress Cover 35,23, 47,55 Emission rate 204.9 Liang and Xu (2014)383
DiNP PVC Flooring 35,23, 47,55 Emission rate 115.3 Liang and Xu (2014)383
DnBP PVC Flooring 35,23, 47,55 Emission rate 119.1 Liang and Xu (2014)383
DEP Latex paint 30,23 Emission rate 28.0 Schripp et al. (2014)358
DnBP Latex paint 30,23 Emission rate 73.9 Schripp et al. (2014)358
in building microenvironments may also be important for exposure clothing as a reservoir for chemicals that can transfer to skin.
to gaseous and particulate contaminants as discussed in Section the equilibrium partition of chemicals to clothing, thereby influencing
entire building. All else being equal, is dust ingestion of SVOCs temperature will influence137,278on the magnitude of the effects.
toddlers, nonintuitively, greater in buildings with warmer surfaces of the It will be valuable to put some bounds
because the dust and air equilibrate faster? The temperature by temperature on exposure is complex and worthy of more study.
used commonly in headspace analysis of materials, water, and other that change over time (cycling) is that contaminants can more rapidly
media. This idea, of course, can be broadened to the temperature move from sources to sinks. Surfaces throughout a building become
mass concentration on the dust will be about the same as for cool more rapidly contaminated (especially for SVOCs) and act ultimately
is dust. This is because the local air concentration (over the flooring to buffer air concentrations, limiting the effectiveness of dilution
as a source) will be much higher in the warm case. This effect and by ventilation. Such buildings can also experience more moisture
quickly for the warm floor. Although partition coefficients condensation problems. The overall effect of building quality
for SVOCs are lower for warm dust, the resulting equilibrium floor, more clothing worn or the extent to which windows are opened. One
will absorb SVOCs from the flooring materials, slowly for the cool interesting effect of temperature gradients or temperatures the
installed heated flooring. Therefore, the floor temperature temperature dynamics to strongly influence exposure. Uncontrolled
some buildings can be substantially greater than others. Why have temperatures also alter occupant activities and behaviors such as
does this matter? Dust that has collected on these surfaces of predictable, such as emissions and partitioning. Therefore, we
comfort, many new or remodeled homes7.5. would expect that daily occupancy cycles that align with
plume and mass-transfer from air to the body surface (Section influence on exposure of some phenomena are somewhat
driving force for dermal uptake. The temperature difference between poorly insulated buildings without adequate heating/cooling, surface
the body surface (skin or clothing) and air influences the thermal and air temperatures vary with day–night cycles and by season. The
activity of compounds in skin surface lipids. Clothing storage ? In buildings where temperatures are generally stable, exposure
the influence of temperature on dermal exposure and transdermal . In should also be relatively stable (after accounting for other effects
overall uptake of chemicals indoors? Temperature certainly influences is such as the rate of outdoor air change or occupant activities)
What8.2fugacity of chemicals building materials, influencing the What are the implications of a poorly controlled indoor climate
). The temperature of the skin influences the chemical
|
predictably periodic as surprisingly large sinks, at least for SVOCs. greenhouse gases were 0.33dioxide, 1.88 ppm for methane, and
a very large capacity be used to control exposure in buildings with 0.18 ppm for carbon 414ppm for nitrous oxide. of the most important
demonstrated for ozone. occupation? Selected building surfaces have 1 the global mean annual concentrations ,2020°C per decade. In
Can temperature449–451to remove gaseous contaminants as Global warming is currently growing at .2019and 1880°C between
design unique materials for such panels as it has been demonstrated temperature rise, sea level rise, extreme weather phenomena. The
that thin organic films naturally develop on surfaces that can act global mean temperature at ground level increased by around
in “regeneration.” It may not even be necessary to the main scenarios are undisputed: global453
from bulk air to surfaces. Consider chilled ceiling panels the contrary, is less well prepared for heavy rain and heat waves.
comfort by radiant cooling. During occupation, cool to transport to region. In Australia, for example, hot periods and heavy al.
not yet equilibrated with indoor air contaminants used to improve regularly. Air conditioning systems are usually installed region
sink, thereby reducing indoor concentrations. During panels that have the desired indoor climate, but a lightweight construction rain occur
non-occupied periods, the panels could be gently heated (or act as a net is common in residential buildings. If there is no rain, droughts to set
simply allowed to rise to background temperature), resulting et al. 456with a high risk of forest fires quickly occur. Central Europe, on
for deposition and low resistance effective sinks for water-soluble gases widely from in excess mortality for the particularly hot year 454–456Steul
this that could be proposed. For73,452simply to the large area available 2003Lindemann et between .2003The effects of climate change vary
air conditioning coils, appear to be are many “thought experiments” like in Germany and found a significant increase 2015and
This is, in large part, due example, very cold zones, such as examined the effects of heat waves159weeks can be compensated.
design259that includes considerations of temperature on exposure. air conditioning systems are still rare in the private sector. The
There source control along with a more comprehensive building region has large water reserves so that dry periods of a few
in the long term the combined goals of comfort, health, and energy performance in older adults during heat waves. Many European
conservation may best be realized with a focus on contaminant houses today have good to very good thermal insulation, but
result in a higher or lower dermal uptake of SVOCs? Addressing on the physical as severe weather. The data for air pollutants in
questions like these may bring some short-termbenefits, but –15of 30Figure found a negative effect of indoor temperature
drains be an effective way to remove pollutants from buildings heavy rain, larger amounts a cloudless day is 125 mm within
? Also, would storing clothing in the warmest part of the home W/m² in summer at noon. Precipitation exceeds –900h is considered
; what about other species and could condensate °C is considered a summer day. The global radiation on251000
typical scenarios New Buildings Energy Act (Gebäudeenergiegesetz).
the temperature the influences of the respective atmosphere for
11|CL IMATE CHANGE shows30Figure in the region of Central Europe. A day on which
to strict thermal 2020for a single-family home have been specified since
different models regarding future climate projections still diverge, thermal requirements buildings and renovation measures must adhere
today and also accepted in the scientific world. Although by the insulation requirements. In Germany, the
The causes and effects of global climate change are well documented are based on the air quality criteria of the European Union. New
Temperature (°C) Precipitation (mm/h) Solar Irradiation (W/m²)

low 0 – 20- <5 low <100 low
medium 25 –0 medium 15 –5 medium 900 –100
high 40 –25 high 25 –15 >900 high
NO2( µg/m³) Air exchange PM10( µg/m³)

< 20 low • manually low10 <
medium 200 –20 • HVAC medium 50 –10
>200 high > 50 high
K))∙Heat transfer coefficient (W/(m²

outer wall0.24
O3( µg/m³) roof0.24 PM2.5( µg/m³)
< 20 low window1.3 <5 low
medium 120 –20 ceilings vs. outdoor air and soil0.24 medium 25 –5
>120 high high 25 >
0 3F I G U R E ranges of temperature, precipitation, and solar irradiation for central Europe. The “high” concentrations of air pollutants O
concept. 3(1 h), NO 2(24 h), and PM 10(24 h) refer to the air quality standards of the European Environment Agency. For PM 2.5,Health Organization.
Energy Saving Regulation (substituted by the German New Buildings Energy Act in 457Typical Organization recently revised its air quality guideline
Please note that the World Health458 )2020the “high” concentration (24 h) refers to the air quality guidelines of the World from the German
The heat-transfer coefficients refer to new buildings and are taken
| 60of 47
35 events will pose significant health challenges for the urban population.
T indo or of further studies come to similar conclusions and predict that future heat
T outd oor
30 that many dwellings are vulnerable to overheating. The authors466,467al.
Salthammer et463to greater temperature extremes. Asumadu-Sakyi et al.
25 overheating. Less well-insulated buildings will fare worse and be subject

Temperature (°C)
- insulated house with manual ventilation will permanently protect against
°C, it is unlikely that even a well30waves with outside temperatures above

20
argue that in the case of heat209,468of Haverinen-Shaughnessy et al.
generally perceived as unpleasant in living rooms. Therefore, the results

15
>30°C were measured in all houses. Large differences in temperature are
the warm season (December–February), maximum temperatures

10
season). The extreme values ranged from <10°C to >37°C. During
°C (warm29°C and 25°C (cool season) or between 22°C and 17between

5 average, the hourly mean indoor temperatures were
01.06.25.05. 08.06. 15.06. 22.06. 29.06. 06.07. 13.07.
houses in the subtropical Brisbane, Australia. On 77measurements in
2021Day + Month
found seasonal differences in temperature469are not surprising.
with higher satisfaction of residents regarding indoor temperature

31F I G U R E in ) and the associated ambient air temperatures
that energy retrofitting of buildings was mostly associated
( 2021summer Temperature profile in a single-family house
DENI011 of the Lower Saxony Air Monitoring Network
data; ambient air temperatures: Station recommendations for heat action plans to protect human health.
( ) . Indoor air temperatures: T. Salthammer (2021), unpublished of previous heat waves, the German government has developed
As a consequence470long-term (installation of air conditioning) measures.
31Figure .2021be avoided during the high-temperature period in June options), medium-term (building-related insulation and cooling), and
waves. Nevertheless, it becomes clear that a rise in temperature cannot distinction is made between short-term (behavior and simple technical
are shaded, windows and doors are kept closed if possible during heat Particular attention is drawn to the need to reduce heat indoors. A
K). The south and south-west windows∙W/(m² 0.35are better than and outdoor air quality and energy consumption.
energy standard. This means that the heat-transfer coefficients 2006the on the room climate, weighing up thermal comfort, clothing, indoor
the nearest measuring station. The house is fully insulated according to and artificial intelligence, an algorithm could, in principle, also decide
The time profile of the ambient air temperature was obtained from.2021 there is a need for ventilation. With the current state of sensor technology
without air conditioning in Braunschweig, Germany, in the summer of the heating when they feel cold and opening the window when they feel
temperature profile in a singlefamily and manually ventilated house to living behavior. So far, many people have been used to turning on
shows the measured question arises whether a paradigm shift is necessary with regard
according to( 30.9°C and a DI of 22.4to a wet-bulb temperature of of smart homes and the heating of houses with renewable energy, the
This corresponds .34%°C with a relative humidity of 34.0period was In view of the growing number471to an improvement in the quality of life.
The highest ambient air temperature measured during the observation47 such concepts find acceptance and whether they can even contribute
equationwhich indicates increasing thermal stress. ,26.9°C and a DI of It will be interesting to see whether
20.0This corresponds to a wet-bulb temperature of .54%humidity of
°C with a relative26.6highest measured indoor air temperature was
), which indicates severe thermal stress. The 12|RESEARCH PR IOR ITI ES

ambient environment and buildings are well understood, air quality.
The fundamentals of heat and mass transfer between459the quality should also consider measuring environmental conditions
the associated temporal trend of ambient air pollutants on indoor within the building shell, in HVAC systems, including their surfaces. air
the influence of climate change and of this living concept are. and building environments. In addition, future studies of indoor
but comparatively460–463Schieweck et al. 464little is published about a great deal about indoor climate in developed countries, but there
smart home, can protect against extreme climatic conditions and are regions of the world without well-documented measurements
high levels of air pollutants, and what the possible disadvantages of indoor temperature and humidity in schools, homes, and other
discussed whether an automated house, a so-called buildings. We will benefit from adding many more measurements
to temperature and here in particular to heat waves. Hamdy et al. of dynamic indoor air and surface temperatures across regions
to illness and death. In their465Dutch case study, the authors showed remains a question worthy of study, partly due to the complexities
Most of research relates discomfort and productivity reduction inherent in such systems. While indoor average temperatures
as an essential cause of several problems ranging from thermal fall within a predictable band, the range within buildings, over
to increase as global warming continues, has been identified time and across the stock of buildings can be broad. We know
point out that overheating in buildings, which is expected The role of temperature in indoor environmental quality
|
exposures influence the epidemiology of fine particle inhalation. as we forecast and plan for a changing outdoor and indoor environment.
in our understanding of these phenomena, it is unclear how indoor develop a more fundamental understanding of these processes, especially
numerous adverse health effects; these relationships have driven not detract from their usefulness. That said, there is value in continuing to
air pollution laws and decades of research. As a major weakness remain empirical in nature. Analogous to the steam engine, this does
of ambient (outdoor) particulate matter (PM) is associated with temperature-related relationships in the indoor sciences
We have long known that the concentration472,473in Section as well as the interplay of building systems and occupation, many
Most exposure to outdoor PM occurs indoors. As discussed9indoors. air velocity. As a result of physical and chemical complexity
as it influences PM chemistry and exposure occurring occupants is a complex interplay of convection, radiation, humidity, and
exposure, toxicology, and epidemiology with indoor thermodynamics within the same structure. The temperature perceived by
a very different chemical and thermodynamic environment. It is vital process ranges from negligible to orders of magnitude, even
that we draw together our current understanding of ambient PM and the extent to which temperature influences an indoor environmental
changes in composition upon entering buildings as it experiences th century. Our buildings are complex19laws were not derived until the
PM of outdoor origin can undergo , th century, even though thermodynamic18by the middle of the
to identify chemically novel and potentially hazardous conditions. were built and operated successfully
rates and has a major impact on indoor environments, exposure, and transport. For many substances, neither the necessary parameters (
studied chemistry. Other behaviors, such as operation of portable heaters by Junge and Pankow to gas/particle equilibria for global atmospheric
in response to a poorly conditioned building, should be can and cannot do. One example concerns the relationships developed
an important example, window-opening increases air change what results, data quality, model assumptions, and calculation methods
account for other environmental quality phenomena. There indoor-related processes very roughly. Consequently, the question arises
is much more to learn about occupant comfort-moderating can therefore be assumed that they often interpret the complex
responses that also influence other indoor phenomena. As in indoor sciences today were originally developed for other purposes. It
Behaviors and building systems (sometimes) work Some of the models usedKOA, ∗) nor their
L
together to control comfort, but infrequently milieu of materials and phases specific to indoor environments.
Because excellent reviews already exist,474,475indoors. parameters, especially those associated with chemical
certainly influence the growth, viability, and diversity of microorganisms should be a focus on improving the quantification of thermodynamic
and other building and environmental factors can be used to make reasonable indoor exposure estimates. There
- related diseases and disease transmission. Temperature, humidity temperature dependencies are sufficiently well known that they
and its influence on microorganisms, pathogens and building changing conditions in the interior as well as the vast diversity
this manuscript does not include a discussion of temperature475kinetics. building environments, offer more scope for interpretation
that protect imbedded pathogens by inhibiting diffusion and disinfection and provide a more rational basis for decision-making. of
proposed that cool, dry conditions favor semisolid respiratory aerosols estimates of uncertainty better represent the constantly
environmental factors. For example, it has recently been comfort, performance and health…". Reasonable the preface to Indoor Air
season and are likely the result of multiple social, building, microbial, and oriented and, as formulated by Fanger and Valbjørn in ,1978climate on man's
Higher transmission rates of viruses have been observed during the cool exist "… to study the effect of indoor are practically
476h 5the installation of fans to achieve an air change of approximately % is much more relevant. Often, seemingly exact results are neither
school facilities. In Germany, a concept is being pursued that provides for realistic nor required tomake decisions. Indoor-related sciences
a great need for intensive ventilation, but this is not even possible in many 20or less than 80%statement whether it is higher than
little thought to the air quality in school classrooms. Suddenly, there is equilibriumshifts with small changes in temperature. The substance is
negligence of the past decades. Despite warnings, authorities had given example, to determine whether an airborne 60%or 50%how this
pandemic has revealed to us the 2particular, the SARS-CoV- particle-bound under given conditions and is often not possible, for
and that society as a whole is poorly prepared for global emergencies. In for the model and measurement uncertainty, diversity of buildings
renovated in many regions, that there is a lack of appropriate ventilation can and the wide range of thermodynamic conditions. This publication
of the recent past have clearly shown that the building stock needs to be uses many examples to show that temperature dependencies
The events−1to concerns about thermal comfort and energy conservation be of an empirical nature and are subject to large uncertainties. It
However, this immediately led .477–479 Representations of measured or modeled indoor phenomena should
conditions on the indoor microbiome and occupant health. provide reasonable estimates of their uncertainties that account
knowledge of the influence of building operation and microenvironmental especially problematic in the context of climate change. In its current
in unpredictable ways. Hence, there is ample room to expand our report, the Intergovernmental Panel on Climate Change (IPCC)
to such emergencies may also alter the microbiology of buildings inherent in understanding our complex building environments are
consequences. Major changes in building operation in response ranges and 480observed regionally and within buildings, the
but should also lead to concerns about unintended challenges these increases appear small compared with the temperature
Historically, many phenomena have been usefully applied with little °C–3.0°C are forecast. While1.2 ,2060For the year .2040°C by 1.9The
understanding of their fundamentals. Famously, steam engines °C1.2assumes a global temperature increase between
| 60of 49
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2021Received: 10 December | 2022Revised: 20 February | 2022Accepted: 13 March

Temperature and indoor environments

Tunga Salthammer1 |Glenn C. Morrison 2

1WKI, Braunschweig, Germany

driven, requiring an appropriate energy balance, sometimes considering ventilation but

is usually accomplished by wearing appropriate clothing, but also the surroundings

rates or dynamic air concentrations, can be the result of complex temperature-dependent

composition of indoor materials. Consequently, emergent phenomena, such as emission

are proportional to the reciprocal of the absolute temperature. It is therefore possible

as diffusion, partitioning equilibria, and chemical reactions, are predictably temperature

From the thermodynamic perspective, the

Indoor Air./10.1111/ina.13022 wileyonlinelibrary.com/journal/ina | 60of 1

indoor hygiene and thermal comfort. Pettenkofer showed what positive

examined the influence of temperature, humidity, and air exchange2

theory, in liquids the law of Stokes-Einstein applies. Furthermore, various

for a short4People who live in temperate climate zones generally

Solid particle Gas phase reaction

Heat and mass

Diffusion in liquid and solid

H2O Hydrolysis H2O

1F I G U R E Dynamics and reactions of a chemical compound ( ) in the indoor environment

uses a cold mixture, freezing water, and body temperature as In

Relative humidity (%)

damage the building structure through drying out, swelling27which or the

3|C S OF CHEMI CAL PROPERTI ES

3.1|pressure and the Clausius–Clapeyron equation

The saturation vapor pressure temperature. The temperature ∆sublH

as constant over a small temperature range. It can also be assumed

K was published by 298the vapor pressure of subcooled liquids at

program interfaces40the hexadecane/air partition coefficient (see Section

) is then used to3Figure ). A new and promising approach is the prediction50use a

B (12) semi-empirical method for the computation of accurate conformer

3.3to calculate a logarithmic partitioning coefficient (see Section under

timating gas/particle distributions. Pankow36assumes

free enthalpyGi with respect to the amount of substance ni to

phases then provides information about the change in the chemical

KPA is the gas/particle distribution coefficient, and ρpart prediction of

Equation(23) according to Harner and Bidleman61is often used. KOA

Calculation methods forZ the publications by Bennett and Furtaw

values51 The poly-parameter LFER approach as described by Goss87

showed that the distribution of an organicequation (27).

Si,A i,B i,L i,and Vi are compound-specific Abraham descriptors.88

as well108Experimental techniques are also applied. discuss have a92

Compound 28PCB- 52PCB- 101PCB- 138PCB- 153PCB- 180PCB-

CAS 7012-37-5 35693-99-3 37680-73-2 35065-28-2 35065-27-1 35065-29-3

logK 9OA 7.85 8.22 8.73 9.66 9.44 10.16

logK 6OA 8.03 8.61 9.22 10.07 9.83 10.59

ΔOAH11( kJ/mol) 74.06 75.29 81.16 88.77 86.97 93.84

ΔOAH12( kJ/mol) 83 86 73.54 87.77 89.90 86.83

therefore tends toward a saturation value. Brunauer, Emmet, and

From the BET isotherm, Junge derived his famousequation (34

equation(35), the parameter cJunge also depends on the temperature

2TA B L E compartments are described

Gas phase and house dust Weschler and Nazaroff (2010)72

Surface and air Wu et al. (2017)133

Growth of organic films Weschler and Nazaroff (2017)73

Building products Bennett and Furtaw (2004)59