2nd stage physical pharmacy II lab

determination of CMC using surface tension

property of Sodium lauryl sulfate
‫ﻣﺨﺘﺒﺮ اﻟﺼﻴﺪﻟﺔ اﻟﻔﻴﺰﻳﺎﺋﻴﺔ اﻟﻤﺮﺣﻠﺔ اﻟﺜﺎﻧﻴﺔ‬

‫ ﺑﺎﺳﺘﺨﺪام ﺧﺎﺻﻴﺔ اﻟﺘﻮﺗﺮ اﻟﺴﻄﺤﻲ ﻟﻜﺒﺮﻳﺘﺎت ﻟﻮرﻳﻞ اﻟﺼﻮدﻳﻮم‬CMC ‫ﺗﺤﺪﻳﺪ‬

UOBCOP
Department of Pharmaceutics
Assistant lect. Mustafa Ragheb
 Surface tension
Surface tension is the force
per unit length (dyne/cm) or
the work per unit area
(ergs/cm2) on the surface of
a liquid that opposes
expansion of the surface
area. /‫ﻣﺴﺎﺣﺔﻃﻮل)إرج‬
‫اﻟﺘﻮﺗﺮ اﻟﺴﻄﺤﻲ ﻫﻮ اﻟﻘﻮة ﻟﻜﻞ وﺣﺪة‬
‫ﺳﻢ( أو اﻟﻌﻤﻞ ﻟﻜﻞ وﺣﺪة‬/‫)داﻳﻦ‬
‫( ﻋﻠﻰ ﺳﻄﺢ اﻟﺴﺎﺋﻞ اﻟﺬي ﻳﻌﺎرض ﺗﻮﺳﻊ‬²‫ﺳﻢ‬
.‫ﻣﺴﺎﺣﺔ اﻟﺴﻄﺢ‬
Methods for determination of surface tension:
I. Drop Weight Method
:‫ﻃﺮق ﺗﺤﺪﻳﺪ اﻟﺘﻮﺗﺮ اﻟﺴﻄﺤﻲ‬
II. Modification of the Drop Weight Method ‫ ﻃﺮﻳﻘﺔ إﺳﻘﺎط اﻟﻮزن‬.1

ً
‫ ﺗﻌﺪﻳﻞ ﻃﺮﻳﻘﺔ وزن اﻟﻘﻄﺮة‬:‫ﺛﺎﻧﻴﺎ‬
III. Capillary Rise Method
‫ ﻃﺮﻳﻘﺔ ارﺗﻔﺎع اﻟﺸﻌﻴﺮات اﻟﺪﻣﻮﻳﺔ‬:‫ﺛﺎﻟﺜﺎ‬

IV. Differential Capillary Height Method ‫ ﻃﺮﻳﻘﺔ ارﺗﻔﺎع اﻟﺸﻌﻴﺮات اﻟﺘﻔﺎﺿﻠﻲ‬.IV

Modification of the Drop Weight Method

• The drop weight method may also be performed by counting the

number of drops (n) in a certain volume of liquid under conditions.
ً ‫ﻳﻤﻜﻦ‬
‫أﻳﻀﺎ إﺟﺮاء ﻃﺮﻳﻘﺔ وزن اﻟﻘﻄﺮة ﻋﻦ ﻃﺮﻳﻖ‬
‫( ﻓﻲ ﺣﺠﻢ ﻣﻌﻴﻦ ﻣﻦ‬n) ‫ﺣﺴﺎب ﻋﺪد اﻟﻘﻄﺮات‬
‫اﻟﺴﺎﺋﻞ ﻓﻲ ﻇﻞ ﻇﺮوف ﻣﻌﻴﻨﺔ‬

where d1 and d2 are densities of liquid 1 and 2. The function F varies only slightly, then:
g 1 v1 d1 V
= And v1 =
g 2 v2 d 2 n1
where V is the volume of each liquid. n1 and n2 are the number of the drops of liquid 1 and 2.
g1 n2 d1
\ =
g2 n1 d 2
Calculate the surface tension of benzene and acetone relative to that of water (72.8 at 25oC).
Procedure of Modification of the Drop Weight
Method ‫إﺟﺮاء ﺗﻌﺪﻳﻞ ﻃﺮﻳﻘﺔ وزن اﻟﻘﻄﺮة‬

.‫ ﻣﻞ ﺑﺎﻟﺨﺮوج ﺑﺒﻂء ﻣﻦ اﻟﻄﺮف‬1 ‫• اﺳﻤﺢ ﻟﻠﺴﺎﺋﻞ اﻟﻤﻜﻮن ﻣﻦ ﻗﻄﺮات‬

• Allow the liquid of 1mL drops slowly from the tip. .(n) ‫ﻋﺪ ﻋﺪد اﻟﻘﻄﺮات‬

• Count the number of drops (n).

• Calculate ϒ1 by using equation below. Where ϒ2 = 72.8 at 25⁰C of
water. ‫ درﺟﺔ‬25 ‫ ﻋﻨﺪ‬Y2 = 72.8 ‫ ﺣﻴﺚ‬.‫ ﺑﺎﺳﺘﺨﺪام اﻟﻤﻌﺎدﻟﺔ أدﻧﺎه‬Y1 ‫اﺣﺴﺐ‬
.‫ﻣﺌﻮﻳﺔ ﻣﻦ اﻟﻤﺎء‬

g1 n2 d1
\ =
g2 n1 d 2
 micelle ‫ﻋﺒﺎرة ﻋﻦ ﻣﺠﻤﻮﻋﺔ ﻣﻦ ﺟﺰﻳﺌﺎت اﻟﻤﺎدة اﻟﺨﺎﻓﻀﺔ ﻟﻠﺘﻮﺗﺮ اﻟﺴﻄﺤﻲ‬
‫اﻟﻤﻨﺘﺸﺮة ﻓﻲ ﻧﻈﺎم ﻏﺮواﻧﻲ ﺳﺎﺋﻞ‬

• is an aggregate of surfactant molecules

dispersed in a liquid colloidal system.
• A typical micelle in aqueous solution forms an
aggregate with the hydrophilic "head" regions
in contact with surrounding solvent, and the
hydrophobic single stail regions are ‫ﺗﺠﻤﻌً ﺎ ﻣﻊ‬ ‫ﻳﺸﻜﻞ اﻟﻤﻴﺴﻴﻞ اﻟﻨﻤﻮذﺟﻲ ﻓﻲ اﻟﻤﺤﻠﻮل اﻟﻤﺎﺋﻲ‬
‫ﻣﻨﺎﻃﻖ "اﻟﺮأس" اﻟﻤﺤﺒﺔ ﻟﻠﻤﺎء ﻋﻠﻰ اﺗﺼﺎل ﺑﺎﻟﻤﺬﻳﺐ‬
sequestered in centre of micelles. ‫ﻟﻠﻤﺎء‬ ‫ وﻳﺘﻢ ﻋﺰل ﻣﻨﺎﻃﻖ اﻟﺬﻳﻞ اﻟﻤﻔﺮدة اﻟﻜﺎرﻫﺔ‬،‫اﻟﻤﺤﻴﻂ‬
‫ﻓﻲ ﻣﺮﻛﺰ اﻟﻤﻴﺴﻴﻞ‬

• This type of micelle is known as a normal-phase

micelle (oil-in-water micelle). ‫ﻳُ ﻌﺮف ﻫﺬا اﻟﻨﻮع ﻣﻦ اﻟﻤﻴﺴﻴﻞ ﺑﺎﺳﻢ اﻟﻤﻴﺴﻴﻞ ﻓﻲ‬
‫اﻟﻄﻮر اﻟﻄﺒﻴﻌﻲ )ﻣﻴﺴﻴﻞ اﻟﺰﻳﺖ ﻓﻲ اﻟﻤﺎء‬
• Inverse micelles have the head groups at the
centre with the tails extending out (water-in-oil
micelle). ‫ﺗﺤﺘﻮي اﻟﻤﻴﺴﻴﻼت اﻟﻌﻜﺴﻴﺔ ﻋﻠﻰ ﻣﺠﻤﻮﻋﺎت رأﺳﻴﺔ ﻓﻲ‬
(‫اﻟﻤﺮﻛﺰ ﻣﻊ اﻣﺘﺪاد اﻟﺬﻳﻞ ﻟﻠﺨﺎرج )ﻣﻴﺴﻴﻠﺔ اﻟﻤﺎء ﻓﻲ اﻟﺰﻳﺖ‬
• Any amphiphilic molecules if present in aqueous media tend to stabilize
themselves by reducing interaction between the non-polar region with water
environment. ‫ﺗﻤﻴﻞ أي ﺟﺰﻳﺌﺎت ﻣﺤﺒﺔ ﻟﻠﻤﺎء إذا ﻛﺎﻧﺖ ﻣﻮﺟﻮدة ﻓﻲ وﺳﻂ ﻣﺎﺋﻲ إﻟﻰ ﺗﺜﺒﻴﺖ ﻧﻔﺴﻬﺎ ﻋﻦ ﻃﺮﻳﻖ ﺗﻘﻠﻴﻞ اﻟﺘﻔﺎﻋﻞ ﺑﻴﻦ‬
.‫اﻟﻤﻨﻄﻘﺔ ﻏﻴﺮ اﻟﻘﻄﺒﻴﺔ وﺑﻴﺌﺔ اﻟﻤﺎء‬
• This stabilization occur by setting themselves in a certain pattern; this pattern is
basically dependent upon the ratio of polar to nonpolar portion if the ration of
polar to non-polar is big à lipid bilayer ‫اﻟﻘﻄﺒﻲ‬ ‫ﻳﺤﺪث ﻫﺬا اﻻﺳﺘﻘﺮار ﻣﻦ ﺧﻼل وﺿﻊ أﻧﻔﺴﻬﻢ ﻓﻲ ﻧﻤﻂ ﻣﻌﻴﻦ؛ ﻳﻌﺘﻤﺪ ﻫﺬا اﻟﻨﻤﻂ ﺑﺸﻜﻞ‬
‫أﺳﺎﺳﻲ ﻋﻠﻰ ﻧﺴﺒﺔ اﻟﺠﺰء اﻟﻘﻄﺒﻲ إﻟﻰ اﻟﺠﺰء ﻏﻴﺮ اﻟﻘﻄﺒﻲ إذا ﻛﺎﻧﺖ ﻧﺴﺒﺔ اﻟﺠﺰء‬
‫إﻟﻰ اﻟﺠﺰء ﻏﻴﺮ اﻟﻘﻄﺒﻲ ﻛﺒﻴﺮة‬
• If the ratio hydrophilic head to the hydrophobic tail is smallà micelles
‫إذا ﻛﺎﻧﺖ ﻧﺴﺒﺔ اﻟﺮأس اﻟﻤﺤﺐ ﻟﻠﻤﺎء إﻟﻰ اﻟﺬﻳﻞ اﻟﻜﺎره ﻟﻠﻤﺎء ﻋﺒﺎرة ﻋﻦ ﻣﻴﺴﻴﻼت ﺻﻐﻴﺮة‬
• Micelles are approximately spherical in shape. Other phases, including shapes
such as ellipsoids, cylinders. ‫ ﺑﻤﺎ ﻓﻲ ذﻟﻚ اﻷﺷﻜﺎل ﻣﺜﻞ اﻟﻘﻄﻊ‬،‫ اﻟﻤﺮاﺣﻞ اﻷﺧﺮى‬.‫• اﻟﻤﺬﻳﻼت ﻟﻬﺎ ﺷﻜﻞ ﻛﺮوي ﺗﻘﺮﻳ ًﺒﺎ‬
‫اﻟﻨﺎﻗﺺ واﻷﺳﻄﻮاﻧﺎت‬

• The shape and size of a micelle depends upon: :‫ﻳﻌﺘﻤﺪ ﺷﻜﻞ وﺣﺠﻢ اﻟﻤﺬﻳﻠﺔ ﻋﻠﻰ‬
1. the molecular geometry of its surfactant molecules ‫ اﻟﻬﻨﺪﺳﺔ اﻟﺠﺰﻳﺌﻴﺔ ﻟﺠﺰﻳﺌﺎت اﻟﻤﺎدة اﻟﺨﺎﻓﻀﺔ ﻟﻠﺘﻮﺗﺮ اﻟﺴﻄﺤﻲ‬.1

2. surfactant concentration, ،‫ ﺗﺮﻛﻴﺰ اﻟﻤﺎدة اﻟﺨﺎﻓﻀﺔ ﻟﻠﺘﻮﺗﺮ اﻟﺴﻄﺤﻲ‬.2

3. temperature, ،‫ درﺟﺔ اﻟﺤﺮارة‬.3

4. pH, ،‫ اﻟﺮﻗﻢ اﻟﻬﻴﺪروﺟﻴﻨﻲ‬.4

5. and ionic strength. ‫ واﻟﻘﻮة اﻷﻳﻮﻧﻴﺔ‬.5

‫• ﻋﻤﻠﻴﺔ ﺗﻜﻮﻳﻦ اﻟﻤﻴﺴﻴﻼت ﺗﻌﺮف ﺑﺎﺳﻢ اﻟﻤﻴﺴﻴﻼت‬

• The process of forming micelles is known as micellization

• When amphiphiles presents in a liquid medium at low
concentration, ‫ﻋﻨﺪﻣﺎ ﺗﻈﻬﺮ اﻟﻤﻮاد اﻟﻤﺤﺒﺔ ﻟﻠﺪﻫﻮن ﻓﻲ وﺳﻂ ﺳﺎﺋﻞ ﺑﺘﺮﻛﻴﺰ ﻣﻨﺨﻔﺾ‬

• the amphiphiles exist separately. ‫ﺗﻮﺟﺪ اﻷﻣﻔﻴﻔﻴﻼت ﺑﺸﻜﻞ ﻣﻨﻔﺼﻞ‬

• As the concentration is increased,

• aggregation occurs over a narrow concentration range
• These aggregates, which may contain 50 or more monomers, are
called micelles. ،‫• ﻣﻊ زﻳﺎدة اﻟﺘﺮﻛﻴﺰ‬
‫ﻳﺤﺪث اﻟﺘﺠﻤﻴﻊ ﻋﻠﻰ ﻧﻄﺎق ﺗﺮﻛﻴﺰ ﺿﻴﻖ‬
.‫ ﺑﺎﻟﻤﻴﺴﻴﻼت‬،‫ ﻣﻮﻧﻮﻣﺮً ا أو أﻛﺜﺮ‬50 ‫ اﻟﺘﻲ ﻗﺪ ﺗﺤﺘﻮي ﻋﻠﻰ‬،‫ُﺗﺴﻤﻰ ﻫﺬه اﻟﺘﺠﻤﻌﺎت‬

• The concentration of monomer at which micelles form is

termed, the critical micelle concentration, or CMC
CMC ‫ﻳُ ﻄﻠﻖ ﻋﻠﻰ ﺗﺮﻛﻴﺰ اﻟﻤﻮﻧﻮﻣﺮ اﻟﺬي ﺗﺘﺸﻜﻞ ﻋﻨﺪه اﻟﻤﻴﺴﻴﻼت اﺳﻢ ﺗﺮﻛﻴﺰ اﻟﻤﻴﺴﻴﻼت اﻟﺤﺮج أو‬
• Most of the physico-chemical property changes can be
used to determine the CMC.
CMC ‫ﻳﻤﻜﻦ اﺳﺘﺨﺪام ﻣﻌﻈﻢ اﻟﺘﻐﻴﺮات ﻓﻲ اﻟﺨﺼﺎﺋﺺ اﻟﻔﻴﺰﻳﺎﺋﻴﺔ واﻟﻜﻴﻤﻴﺎﺋﻴﺔ ﻟﺘﺤﺪﻳﺪ‬

• Below CMC concentration, when no micelles are present,

the substance behaves in a similar way to other
electrolytes, the various properties being relates to the
concentration of the substance.
‫ ﺗﺘﺼﺮف اﻟﻤﺎدة ﺑﻄﺮﻳﻘﺔ ﻣﻤﺎﺛﻠﺔ‬،‫ ﻋﻨﺪﻣﺎ ﻻ ﺗﻮﺟﺪ ﻣﻴﺴﻴﻼت ﻣﻮﺟﻮدة‬،CMC ‫ﺗﺤﺖ ﺗﺮﻛﻴﺰ‬
‫ ﺣﻴﺚ ﺗﺮﺗﺒﻂ اﻟﺨﺼﺎﺋﺺ اﻟﻤﺨﺘﻠﻔﺔ ﺑﺘﺮﻛﻴﺰ اﻟﻤﺎدة‬،‫ﻟﻐﻴﺮﻫﺎ ﻣﻦ اﻟﺸﻮارد‬

• Above this concentration, the properties are not simply

related to concentration. ‫ اﻟﺨﺼﺎﺋﺺ ﻻ ﺗﺮﺗﺒﻂ ﻓﻘﻂ ﺑﺎﻟﺘﺮﻛﻴﺰ‬،‫ﻓﻮق ﻫﺬا اﻟﺘﺮﻛﻴﺰ‬

• Thus, for example, a graph of surface tension against ‫ ﺳﻮف ﻳﻈﻬﺮ اﻟﺮﺳﻢ اﻟﺒﻴﺎﻧﻲ‬،‫ﻋﻠﻰ ﺳﺒﻴﻞ اﻟﻤﺜﺎل‬
concentration for series of solutions of the colloidal ‫ﻟﻠﺘﻮﺗﺮ اﻟﺴﻄﺤﻲ ﻣﻘﺎﺑﻞ اﻟﺘﺮﻛﻴﺰ ﻟﺴﻠﺴﻠﺔ ﻣﻦ‬
‫ﺣﻠﻮل اﻹﻟﻜﺘﺮوﻟﻴﺖ اﻟﻐﺮواﻧﻲ ﺗﻐﻴﺮًا ﻓﻲ اﻟﻤﻨﺤﺪر‬
electrolyte will show a change of slope at the critical .(CMC) ‫ﻋﻨﺪ ﺗﺮﻛﻴﺰ اﻟﻤﻴﺴﻴﻞ اﻟﺤﺮج‬

micelle concentration, (CMC).

What are other properties can be used to Determine the
CMC???
Q/ explain why. The surface tension of any amphiphilic
substance starts to stop reduction and stays constant beyond
the CMC. ‫ﺛﺎﺑﺘﺎ ﺑﻌﺪ‬
ً ‫اﺷﺮح ﻟﻤﺎذا ﻳﺒﺪأ اﻟﺘﻮﺗﺮ اﻟﺴﻄﺤﻲ ﻷي ﻣﺎدة ﻣﺤﺒﺔ ﻟﻠﺪﻫﻮن ﺑﺎﻟﺘﻮﻗﻒ ﻋﻦ اﻻﺧﺘﺰال وﻳﺒﻘﻰ‬
CMC
• Before CMC, the surfactant tends to remain at the interfacial surface
and reduces the surface tension with increase the concentration until
it reaches the CMC the micelles starts to form. In this range the
interface is saturated with surfactant molecules and the continued
reduction in the surface tension is mainly due to the increased
activity of the surfactant in the bulk, rather than at the interface.
‫ ﻳﻤﻴﻞ اﻟﻌﺎﻣﻞ اﻟﺨﺎﻓﺾ ﻟﻠﺘﻮﺗﺮ‬،CMC ‫ﻗﺒﻞ‬
‫اﻟﺴﻄﺤﻲ إﻟﻰ اﻟﺒﻘﺎء ﻋﻠﻰ ﺳﻄﺢ اﻟﻮاﺟﻬﺔ‬
‫وﻳﻘﻠﻞ ﻣﻦ اﻟﺘﻮﺗﺮ اﻟﺴﻄﺤﻲ ﻣﻊ زﻳﺎدة اﻟﺘﺮﻛﻴﺰ‬
‫ ﺣﻴﺚ ﺗﺒﺪأ اﻟﻤﻴﺴﻴﻼت‬CMC ‫ﺣﺘﻰ ﻳﺼﻞ إﻟﻰ‬
‫ ﻓﻲ ﻫﺬا اﻟﻨﻄﺎق ﺗﻜﻮن اﻟﻮاﺟﻬﺔ‬.‫ﻓﻲ اﻟﺘﻜﻮن‬
‫ﻣﺸﺒﻌﺔ ﺑﺠﺰﻳﺌﺎت اﻟﻌﺎﻣﻞ اﻟﺨﺎﻓﺾ ﻟﻠﺘﻮﺗﺮ‬
‫اﻟﺴﻄﺤﻲ وﻳﻌﻮد اﻻﻧﺨﻔﺎض اﻟﻤﺴﺘﻤﺮ ﻓﻲ‬
‫اﻟﺘﻮﺗﺮ اﻟﺴﻄﺤﻲ ﺑﺸﻜﻞ أﺳﺎﺳﻲ إﻟﻰ زﻳﺎدة‬
‫ﻧﺸﺎط اﻟﻌﺎﻣﻞ اﻟﺨﺎﻓﺾ ﻟﻠﺘﻮﺗﺮ اﻟﺴﻄﺤﻲ ﻓﻲ‬
.‫اﻟﻜﺘﻠﺔ وﻟﻴﺲ ﻋﻠﻰ اﻟﻮاﺟﻬﺔ‬
 Procedure:

‫ﺗﺤﻀﻴﺮ ﺗﺮﻛﻴﺰات ﻣﺨﺘﻠﻔﺔ ﻣﻦ ﻛﺒﺮﻳﺘﺎت ﻟﻮرﻳﻞ‬ ‫ﻗﻢ ﺑﻘﻴﺎس اﻟﺘﻮﺗﺮ اﻟﺴﻄﺤﻲ ﻟﻬﺬه اﻟﻤﺤﺎﻟﻴﻞ‬ CMC ‫ اﻟﺘﺮﻛﻴﺰ وﺣﺪد‬% ‫ ﻣﻘﺎﺑﻞ‬Y ‫ارﺳﻢ‬
،٪0.2 ،٪0.1 ،٪0.075 ،٪0.05 ،٪0.005 ،‫اﻟﺼﻮدﻳﻮم‬ ‫ﺑﺎﺳﺘﺨﺪام ﻃﺮﻳﻘﺔ وزن اﻟﻘﻄﺮة اﻟﻤﻌﺪﻟﺔ‬
.٪0.5 ‫ و‬،٪0.4 ،٪0.3

1 2 3
Prepare different Measure the surface Plot ϒ1 versus
concentration of sodium tension of these solutions %concentration and
laurayl sulfate, 0.005%, by using the modified drop determine the CMC.
0.05%, 0.075%, 0.1%, 0.2%, weight method.
0.3%, 0.4%, and 0.5%.