2.

4 Solubility of gases in liquids

The amount of gas which can be dissolved by
a particular liquid depends on the temperature,
the pressure and the nature of both the
gas and the liquid solvent. The solubility may
be expressed by Bunsens absorption coefficient,
a, which is the volume of gas reduced to 273 K
and a pressure of 1 bar which dissolves in a
unit volume of the liquid at the given temperature
when the partial pressure of the gas is
1 bar.
EXAMPLE 2.4 Calculation of the Bunsen

absorption coefficient

If the solubility of N_2 in water at 25C and a

nitrogen pressure of 450 torr is 0.378 mol m_03,
calculate the Bunsen coefficient.
Answer
The volume, V, of dissolved nitrogen at 0C
and a pressure of 760 torr (1.013 " 10_5Nm_02),
assuming ideality, is given by equation (2.1) as
The volume of N_2 that would dissolve at a
nitrogen pressure of 760 torr is
That is, the Bunsen absorption coefficient for
N_2 at 25C is 0.0143.
In anaesthetic practice, an alternative solubility
coefficient, the Ostwald solubility coefficient,
is preferred. This coefficient is defined as the
volume of gas which dissolves in a unit volume
of the liquid at the given temperature. The
volume of gas is not corrected to standard temperature
and pressure but instead is measured
at the temperature and pressure concerned.
The important difference between these two
coefficients is that the Ostwald coefficient is
independent of pressure, as we can see from
the following example.
Consider a closed vessel containing 1 dm_3
(1 litre) of water above which is nitrogen at a
pressure of 1 bar at room temperature. The
volume of nitrogen dissolved at equilibrium is
0.016 dm_3. If the pressure is increased to 2 bar
at the same temperature, then the amount of
nitrogen which dissolves is doubled, according
to Henrys law (see section 2.4.2). The resultant
volume of nitrogen dissolved is 0.032 dm_3
when measured at 1 bar but 0.016 dm_3 when
measured at the ambient pressure of 2 bar
(according to the ideal gas law). Consequently,
the volume of nitrogen dissolved measured at
ambient pressure, and hence the Ostwald coefficient,
remains unchanged even though the
partial pressure of the nitrogen and also the
number of dissolved molecules are doubled.
2.4.1 Effect of temperature on solubility
When gases dissolve in water without chemical
reaction there is generally an evolution of
heat. Hence by Le Chateliers principle an
increase in temperature usually leads to a

decreased solubility. The effect of temperature

on the absorption coefficient may be determined
from an equation analogous to the
vant Hoff equation:
(2.16)
where a_1 and a_2 are the absorption coefficients
at temperature T1_ and T2_ , respectively, and H
is the change in enthalpy accompanying the
solution of 1 mole of gas.
A practical illustration of the decreased solubility
of gases with increase of temperature is
the appearance of gas bubbles on the sides of a
vessel containing water when the vessel is
heated; the water is saturated with air at lower
temperatures and the amount of air that it can
contain decreases with increase of temperature,
resulting in bubble formation.
2.4.2 Effect of pressure on solubility
The influence of pressure on solubility is
expressed by Henrys law, which states that
2.5 The solubility of gases in blood and
tissues
The application of physicochemical principles
in the consideration of the solubility of gases
in blood and tissues is complicated by the
complex nature of these solvent systems.
2.5.1 The solubility of oxygen in the blood
The major respiratory function of the lungs is
to add oxygen to the blood and to remove
carbon dioxide from it. Thus the measurement
of the concentration of these gases in the
arterial blood leaving the lungs, combined
with a knowledge of the partial pressure of
oxygen in the inspired air (approximately
147 torr at 37C), allows an assessment of the
gas exchanging function of the lungs.
The solubility of oxygen in the blood is
dependent upon the concentration of haemoglobin,
each gram of which can combine with
1.34 cm_3 of oxygen at 37C, and upon the
presence of other ligands which combine with
haemoglobin and affect oxygen binding. The
oxygen saturation, , of a particular blood
sample, which determines the colour of the
blood, is defined by the ratio of the oxygen
concentration in the blood sample to the
oxygen concentration when that blood is fully
saturated (i.e. the oxygen capacity of the
blood). Defined in this manner, it is clear that
for an anaemic patient, where there is a
low haemoglobin content, may be the same as
that for a patient with polycythaemia, but the
oxygen concentration of the blood would be
much less in the anaemic patient.
The partial pressure, , of the oxygen in
the blood (oxygen tension) is related to by
the oxygen dissociation curve (Fig. 2.11). The

shape and position of this sigmoidal curve

depend on the temperature, the hydrogen ion
concentration and the concentration within
the red cells of other ligands of haemoglobin
Influence of body temperature

Temperature also influences anaesthetic solubility;

temperature increase leads to a decrease
in solubility as expected from section 2.4.1.
Table 2.4 shows the temperature coefficients
of the both water_gas, _water_gas, and oil_gas,
_oil_gas, partition coefficients for a range of
anaesthetic gases.
These data are relevant clinically because of
possible wide variation of body temperature in
the surgical patient. Body temperature may be
lowered as a result of preoperative sedation, by
cutaneous vasodilation, by the infusion of
cold fluids and by reduced metabolism under
operating conditions. The increase in oil_gas
partition coefficient with decreasing temperature
means that the effective concentration at
the hydrophobic site of action is increasing
and hence the apparent potency of the anaesthetic
increases.
Summary
Raoults law can be used to calculate the
partial pressure of a component in the
vapour phase above a liquid under conditions
of equilibrium if the composition of
the liquid is known and if the system is
assumed to be ideal. Mixtures of the hydrofluoroalkane
propellants HFA 134a and
HFA 227 obey Raoults law over a wide
concentration range, but positive deviations
from this law occur when the cosolvent
alcohol is included in the formulation.
The variation of vapour pressure with temperature
is described by the Clausius__
Clapeyron equation; an equation, which
provides a useful method for the experimental
determination of the enthalpy
changes accompanying phase transitions.
The relative lowering of the vapour pressure
following the addition of a solute to a
solvent is equal to the mole fraction of the
solute. A consequence of this change of
vapour pressure is that the boiling point of
the solution is increased and its freezing
point decreased.
The solubility of a gas in a liquid may be
expressed by the Ostwald solubility coefficient,
which is the volume of gas dissolved
in unit volume of liquid at a given temperature,
or as the Bunsens absorption coefficient,
in which the temperature and
pressure are reduced to standard conditions.
The solubility of a gas in a liquid decreases

with increase of temperature at constant

pressure and is directly proportional to
pressure at a constant temperature (Henrys
law).
Application of temperature and pressure
relationships in the prediction of the solubility
of anaesthetic gases in vivo is complicated
by the interaction of these gases with
the lipids and proteins in the blood and in
tissue fluids.

2.5 Kelarutan gas dalam darah dan

jaringan
Penerapan prinsip-prinsip fisika
dalam pertimbangan kelarutan gas
dalam darah dan jaringan yang rumit oleh
sifat kompleks dari sistem pelarut.
2.5.1 Kelarutan oksigen dalam darah
Fungsi pernapasan utama paru-paru adalah
untuk menambah oksigen ke dalam darah dan untuk menghapus
karbon dioksida dari itu. Dengan demikian pengukuran
konsentrasi gas-gas ini di
darah arteri meninggalkan paru-paru, dikombinasikan
dengan pengetahuan tentang tekanan parsial
oksigen dalam udara inspirasi (sekitar
147 torr pada 37 C), memungkinkan penilaian terhadap
gas bertukar fungsi paru-paru.
Kelarutan oksigen dalam darah
tergantung pada konsentrasi hemoglobin,
setiap gram yang dapat menggabungkan dengan
1,34 cm_3 oksigen pada suhu 37 C, dan pada
kehadiran ligan lain yang menggabungkan dengan

hemoglobin dan mempengaruhi oksigen mengikat. Itu

saturasi oksigen,, dari darah tertentu
sampel, yang menentukan warna
darah, didefinisikan oleh rasio oksigen
konsentrasi dalam sampel darah ke
konsentrasi oksigen ketika darah yang sepenuhnya
jenuh (yaitu kapasitas oksigen dari
darah). Didefinisikan dengan cara ini, jelas bahwa
untuk pasien anemia, di mana ada
kadar hemoglobin rendah, mungkin sama dengan
bahwa untuk pasien dengan polisitemia, tetapi
konsentrasi oksigen dari darah akan
apalagi pada pasien anemia.
Tekanan parsial,, oksigen di
darah (tekanan oksigen) adalah terkait dengan dengan
kurva disosiasi oksigen (Gambar. 2.11). Itu
bentuk dan posisi kurva sigmoidal ini
tergantung pada suhu, ion hidrogen
konsentrasi dan konsentrasi dalam
sel-sel merah ligan lain hemoglobin
Pengaruh suhu tubuh
Suhu juga mempengaruhi kelarutan anestesi;
Peningkatan suhu menyebabkan penurunan
kelarutan seperti yang diharapkan dari bagian 2.4.1.
Tabel 2.4 menunjukkan koefisien suhu
dari kedua water_gas, _water_gas, dan oil_gas,

_oil_gas, koefisien partisi untuk berbagai

gas anestesi.
Data-data ini secara klinis relevan karena
mungkin variasi suhu tubuh di
pasien bedah. suhu tubuh mungkin
menurunkan akibat sedasi pra operasi, oleh
vasodilatasi kulit, dengan infus
cairan dingin dan metabolisme berkurang di bawah
kondisi operasi. Peningkatan oil_gas
koefisien partisi dengan suhu menurun
berarti bahwa konsentrasi efektif
situs hidrofobik aksi meningkat
dan karenanya potensi nyata dari obat bius
meningkatkan.
Ringkasan
hukum Raoult dapat digunakan untuk menghitung
tekanan parsial komponen dalam
fasa uap di atas cairan dalam kondisi
kesetimbangan jika komposisi
cairan dikenal dan jika sistem ini
diasumsikan ideal. Campuran dari hydrofluoroalkane yang
propelan HFA 134a dan
HFA 227 mematuhi hukum Raoult lebih lebar
Kisaran konsentrasi, tetapi penyimpangan positif
dari hukum ini terjadi ketika cosolvent yang
alkohol termasuk dalam formulasi.

 Variasi tekanan uap dengan temperatur

dijelaskan oleh Clausius _-_
persamaan Clapeyron; persamaan, yang
memberikan metode yang berguna untuk eksperimental
penentuan entalpi
Perubahan yang menyertai transisi fase.
relatif Penurunan tekanan uap
berikut penambahan zat terlarut ke
pelarut sama dengan fraksi mol dari
zat terlarut. Sebagai konsekuensi dari perubahan ini
tekanan uap adalah bahwa titik didih
larutan ditingkatkan dan bekunya
Titik menurun.
Kelarutan gas dalam cairan mungkin
diungkapkan oleh koefisien kelarutan Ostwald,
yang volume gas terlarut
di unit volume cairan pada suhu tertentu,
atau sebagai koefisien penyerapan Bunsen,
di mana suhu dan
tekanan dikurangi dengan kondisi standar.
Kelarutan gas dalam penurunan cair
dengan kenaikan suhu konstan
tekanan dan berbanding lurus dengan
tekanan pada suhu konstan (Henry
hukum).
Aplikasi temperatur dan tekanan

hubungan dalam prediksi kelarutan

gas anestesi in vivo rumit
oleh interaksi dari gas-gas ini dengan
lipid dan protein dalam darah dan di
cairan jaringan.