‫لجنة كليةالصيدلة ~ كتلة االتحاد االسالمية‬

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 ‫لجنة كليةالصيدلة ~ كتلة االتحاد االسالمية‬

Monolayer at Liquid Surface

** Depends on solubility of adsorbate in the liquid subphase

(Adding surfactant to the system).

Soluble Insoluble

Important Parameters:
For soluble mono layer have surface tension
 Surface tension ().

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 ‫لجنة كليةالصيدلة ~ كتلة االتحاد االسالمية‬

 Surface Excess (  ): amount of amphiphile

per unit area of surface in excess of that in the bulk of the liquid.(this new
term is very easy

** Imagine if we have 1 cm square (‫ )مربع‬on the surface and 1 cm square in bulk

The difference between

the two Squares equal the
surface excess

 Concentration (C ): concentration of amphiphile in the bulk of the liquid

(from the certain volume ).

• Pharmaceutical interest: ( from the book )

– Emulsions are stabilized by the presence of an interfacial film

between oil and water phases.

– Knowledge of the area occupied by each amphiphilic molecule at

the interphase is important in achieving optimum stability of
the emulsion.

– The efficiency of wetting and detergent processes depends on

the concentration of the material adsorbed.

– Monolayers of adsorbed amphiphiles can be used as in vitro

models for biologic membranes that are thought to consist of
two monolayers placed back to back with the hydrocarbon
chains intermeshed.

– Provide valuable information on the dimensions of molecules

because it is possible to calculate the area occupied by
amphiphilic molecules.
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 ‫لجنة كليةالصيدلة ~ كتلة االتحاد االسالمية‬

Soluble Monolayers and Gibbs Adsorption Equation

 The addition of amphiphiles to a liquid system leads to a reduction in surface
tension owing to these molecules or ions being adsorbed as a monolayer.

2=-(1/RT)(d /dlnC2)

2 : Surface excess or surface concentration that is the amount of the

amphiphile per unit area of surface in excess of that in the bulk of the liquid

C2 : is the concentration of amphiphile in the liquid bulk

R: the gas constant

T: absolute temperature

 To calculate dƔ/dlnC draw the relation

between surface tension and linC2

A-B: reduction curve

B-D: linear decline

D: cmc

D-E: horizontal "at which the surface

tension will be constant"

Now  From any portion at (B-D) we can find slope which will equal dƔ/dlnc2

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 ‫لجنة كليةالصيدلة ~ كتلة االتحاد االسالمية‬

 In order to calculate the surface area of each

molecule from this diagram please follow this steps :
1 ) Slope =

2) 2=-(1/RT)*Slope

This is mole/SA; in order to convert from mole to molecule we multiply it by

Avogadro's number

3) 2*Avogadro's number = molecule / SA

4) SA(surface area)/molecule = 1 / Step number 3

Unit: cm2/molecule

Insoluble Monolayer and Film Balance

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 ‫لجنة كليةالصيدلة ~ كتلة االتحاد االسالمية‬

 If the film on surface condensed area of film known volume of liquid known ,
Mwt known, density known).

1) Find the thickness of the film (h) =

2) Find the surface area:

- Weight (w) = volume (V) × density ( )

- Moles (n) = =

- Total number of surfactant molecules = moles (n) × Avogadro's number (N)

= ×N

- Surface area/ molecule =

M: Molecular weight
S: Surface tension
V: Volume

Expect one question on this idea 

Memorize only the equation which in the Bold font

Langmuir, Adam, Harkins Film Balance

• Quantitative properties of the film that is spread over a clean surface. (trough).

• Surface Film Pressure()=compressive force per unit area on the float.

• = 0- 

0 : surface tension for the solvent before adding the surfactant

 : surface tension for the solvent after adding the surfactant

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 ‫لجنة كليةالصيدلة ~ كتلة االتحاد االسالمية‬

Effect Of Surfactant On Surfce:

- From the film pressure we can get curve and from the curve
directly know SA/Molecule 

- This method is automated and make correlation between (surface

pressure with SA) mean SA for all situation for tail .

extrapolation ‫ وبعمل‬medial portion ‫رح يطلع معنا مجموعه نقاط و بنروح على‬

SA/Molecule ‫ورح ييطلع عندي‬

‫هال في االمتحان اذا شفت رسمه مثل الموجود في الساليد اعرفو امتداد الخط المستقيم مع‬
‫المحور السيني بعطي‬

SA/Molecule

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 ‫لجنة كليةالصيدلة ~ كتلة االتحاد االسالمية‬

 Surface Area: increase expansion and break

interface with H-bond and Van der Waal forces.

 Substrate dissolved in a volatile solvent

(hexane).

Phase Changes When insoluble film is spread on the surface :

Now 
we will talk deeper in gaseous state.. at gas state SAA molecule are very wide from
each other,, when we pressed them the distance between them decrease then it
will turns to state in between called liquid expanded state and when pressed
more it will be at a state called liquid condensed state (the most powerful state
because distance between them as we need in emulsion and maintained their
elasticity) when pressed more it will be as a solid state like gelatin

‫المهم هون تعرفوا انه المنطقه اللي بنشتغل‬

Liquid condensed and ‫عليها هي‬
the extrapolation with x-axis
will Give SA/Molecule

‫واخيرا ادعو هللا ان يوفقكم جميعا ويسهل اموركم ويكتب لكم الخير اينما ذهبتهم ويرزقكم‬
‫الذاكرة القوية والعمل الصالح والعالمات العالية ورضا الوالدين وان شاء هللا تجيبو عالمات‬
‫اعلى من الفيرست وال تبخلو علي بالدعاء بظهر الغيب وعقبال ما نشوفكم كلكم متخرجين‬

‫زميلتكم شروق المومني‬

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 ‫لجنة كليةالصيدلة ~ كتلة االتحاد االسالمية‬

 Adsorption at Solid Interfaces:

 What is the difference between adsorption and absorption?

Adsorption: Molecules adhere to the surface of the phase.

Absorption: Molecules are drawn into the bulk of the phase.

If you want study the adsorption into the liquid state from the gaseous state to
liquid state or to the solid state, we can see many applications for the adsorption.
For example:

In the gas adsorption it can be use in:

 Removable of odors.
Ex. Uses of charcoal to remove the refrigerator smell.

 Gas masks.
Its adsorbent with huge surface area which adsorb the material before
inhaling it by your nose.

 Measurement of particle dimensions.

In the Solid/Liquid adsorption:

 Decolorizing solution. ) ‫(تنقية‬

In the purification of water at the initial step, there is an adsorbent that
adsorb any colorizing agent.

 Adsorption chromatography.
To separate the material from each other.

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 ‫لجنة كليةالصيدلة ~ كتلة االتحاد االسالمية‬

(Non-polar medial make adsorption for the non-polar drug / polar media
make adsorption for polar drug and so on )

 Detergency.(‫(التنظيف‬

 Wetting.

 Why Adsorption Occur?

This is the method for solid to decrease surface free energy for the system, so
increase the thermodynamic stability.

 Solid-Gas Interface:
The degree of adsorption of a gas by a solid depends
on:

• Physicochemical properties (type) of

adsorbent and adsorbate. Adsorbent: the material
used to adsorb the gas.
• Surface area of adsorbent.
Increase surface area will increase the adsorption. Adsorbate: the substance
being adsorbed.
• Temperature.
In the gas:
Increase the temperature will increase the tendency of the vaporization,
and decrease the adsorption.

In the liquid - solid we can’t judge.

• Partial Pressure of Gas.

Increase the pressure of gas will increase the adsorption. But not forever, it
depends on the type of the material
For example if we have a solid material the adsorbent may form a mono-
layer on the surface then the adsorption will stop and maybe it is continue
to form a second layer and if this solid is porous then the adsorbent go
inside this pores

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 ‫لجنة كليةالصيدلة ~ كتلة االتحاد االسالمية‬

• Purity of adsorbent.
Increase the purity will increase the adsorption.
- Like if we use activated charcoal " pure charcoal "for adsorption of the
drug in drug poisoning conditions

• Type of adsorption:
Chemisorptions: the adsorbate
 Chemical (irreversible, chemisorptions). is attached to the adsorbent by
primary chemical bonds.
 Physical (Reversible, desorption).
Ex. Van Der Waals forces. Desorption: the removal of the
adsorbate from the adsorbent.

 Adsorption Isotherm:
Is the relationship between the amounts of gas physically adsorbed on a solid and
the equilibrium pressure or concentration at constant temperature
[The term isotherm refers to a plot at constant temperature]

 Type I Isotherm:

Increase pressure will increase the adsorption, until it

will stabilize at certain point.

There are two methods to describe this type:

1. Freundlich Isotherm:

Freundlich suggested this relationship:

• Y: mass of gas (x) adsorbed per unit mass (m) of adsorbent.

• K, n: constants.

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 ‫لجنة كليةالصيدلة ~ كتلة االتحاد االسالمية‬

And to convert this equation to linear equation,

we can use the logarithm.

Slope = 1/n

Intercept = Log K

In the exam the doctor will give us the figure. And from
it we calculate the freundlich constants [K & n].

2. Langmuir:

Developed an equation based on the theory that the molecules or atoms of gas
are adsorbed on active sites of the solid to form a layer one molecule thick
(monolayer).

Y = x/m
Ym: it’s (x/m) when one monolayer completed. [It’s constant]
b: constant
p: pressure

When convert the equation to linear equation

, it will be:

Slope = 1/Ym

Intercept = 1/bYm

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 ‫لجنة كليةالصيدلة ~ كتلة االتحاد االسالمية‬

 What applies for gas applies for liquid but instead of P (pressure) we put C
(concentration)

 Type II Isotherm:

- It’s sigmoidal shape and occurs when gases adsorbed onto

non-porous solid to form monolayer followed by multilayer
formation.

- First inflection point represents the formation of monolayer.

[The first monolayer finishes at the plateau]

- This type is best described by an expression derived

Brunauer, Emmett, and Teller (BET).

" ‫" اسم المعادلة كثير مهم‬

- This equation can be written as:

b: constant proportional to the difference between heat of adsorption of gas

in the first layer and latent heat of condensation of successive layers. (b>2)

 When one monolayer formed BET reduced to Langmuir equation (the simplest
case), so it can use to describe both type I and type II.

 Type III:

It results when (b) is less than 2 (b <2 ) in the BET

expression.

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 ‫لجنة كليةالصيدلة ~ كتلة االتحاد االسالمية‬

 Type IV:

- It’s typical of adsorption onto Porous solids.

[It distinguish characteristic for type IV]

- So we can judge the porosity of the material from this

type.

- First infliction point when monolayer completed.

- Followed by condensation inside pores and multilayer

formation.

 Type V:

- Few instances.

- When heat of vaporization in the first layer is less than

heat of condensation of successive layers.

- Show capillary condensation.

Type IV and type V used for porous solids and show

capillary condensation, but the difference; is the condensation
inside pores occur when the monolayer completed in the type
IV, but in type V the condensation inside pores occur at the
same time with the first monolayer.

 Type IV and V frequently involve hysteresis loop.

 Total surface area can be obtained from those contain 1

monolayer completed. (Type 1 and Type 2, and type 4).

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 ‫لجنة كليةالصيدلة ~ كتلة االتحاد االسالمية‬

 How get total surface area?

TSA=Total number of molecules × cross sectional area of each molecule.

Specific surface area = surface area/unit weight adsorbent.

 Solid-Solid interface:
- Adsorption of a fine cohesive powder at the surface of a coarse free flowing
ordered mixtures.

- Such as dry blend of sucrose and antibiotics.

 Wetting:
- The wettability in the pharmaceutical field
expressed by wetting angle theta (θ).

- Whenever θ increases the wettability decreases.

- So the maximum wettability is obtained when

(θ = 0)

- SAA is used as wetting agent.

- Detergency involves wetting step of dirts.

 Uses of SAA:
• Emulsifying agent. (O/W) & (W/O)

• Detergents.

• Wetting Agents.

• Solubilizing agents.

• Antibacterial : Cationic (+) SAA act as antibacterial drug.

• Affect drug activity.

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 ‫لجنة كليةالصيدلة ~ كتلة االتحاد االسالمية‬

‫‪• Affect drug activity: penetration hexylresorcinol into pinwarm ascaris.‬‬

‫‪• Foaming agent.‬‬

‫‪• Antifoaming agent.‬‬

‫" ارسم حلمك‪..‬لونه‪..‬واصنع منه مقاسا كبيرا لجدار غرفتك‪..‬‬

‫ونسخة صغيرة لمكتبك اكتبه علي المرآة كي تراه صباحا‪..‬‬

‫وأعلي فراشك كي يلقي عليك تحية المساء قبل ان تنام "‬

‫كريم الشاذلي ‪,‬افكار صغيرة لحياة كبيرة‬

‫سامحونا على ما بدر مننا من أخطاء ‪‬‬

‫زميلكم عمر الكردي‬

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