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DISPERSED SYSTEMS
Ingrid Žitňanová
DISPERSED SYSTEMS
Dispersed
phase
(water)Dispersionmedium
(oil)
SOLUTE
(DISPERSED PHASE )
SOLVENT
(DISPERSION MEDIUM )
Solute (NaCl) Solvent (water)
It has a non-uniform composition
There are two or more phases
They can be separated out physically
It has a uniform composition
It has only one phase
It can’t be separated out physically
Classification of the dispersed systems
according to the diameter of dispersed particles
1. Analytical (molecular, true solutions)
2. Colloids
3. Coarse / Crude dispersion (suspension)
< 1 nm
1 – 1000 nm
> 1000 nm
SolutionColloidsSolution Coarse dispersion
particle sizeType of dispersion
Properties of the dispersed systems
Dispersion Molecular (true solut.) Colloidal Coarse (crude)
Particles size 1 nm 1 – 1000 nm > 1000 nm (1 μm)
Particles Filterability Cannot be separated by
filtration
Can be separated by
semipermeabile
membrane
Can be separated by
filtration
Diffusion of particles rapid slow No diffusion
Visibility of particles Not visible under the
electrone microscope
Can be visible under
the electrone
microscope
Can be seen under
the low power
microscope or eye
Sedimentation of
particles
Particals do not sediment Sediment in the
strong centrifugal
field
Sediment under the
influence of gravity
Optical properties Transparent
No Tyndall effect
Tyndall effect Not transparent
Tyndall´s effect
is due to the scattering of light by colloidal particles, while showing
no light in a true solution.
This effect is used to determine whether a mixture is a true solution
or a colloid.
True
solution
Colloidal
solution
• when light is passed
through a colloidal
solution, the substance
in the dispersed phases
scatters the light in all
directions, making it
readily seen
TRUE SOLUTIONS(Analytical, molecular solutions)
TRUE SOLUTION
• a homogeneous mixture of two or more components
• particle size 1 nm
Liquid (vinegar)
Gas (carbon dioxide)
Solid (sugar)
e.g. water Acetic acid in water
CO2 in water
Sugar water
+
SolventsPolar
Nonpolar
Solutes
Polar
Nonpolar
• Polar solutes dissolve well in polar solvents
• Nonpolar solutes dissolve well in non-polar solvents
– e.g.water, ethanol, methanol,
– e.g. chloroform, hexane, benzene
- glucose, acetic acid, NaCl
- fats, steroids, waxes
Oil in water
Electrolytes, Nonelectrolytes
In water,
Strong electrolytes separate into ions making solutions that conduct electricity
Weak electrolytes produce a few ions
Nonelectrolytes produce molecules, not ions, do not conduct electricity
Electrolyte – when dissolved in water separates into cations and anions,
which disperse uniformly through the solvent.
Strong electrolytes
are compounds with ionic or very polar covalent bond
strong electrolyte
when dissolved in water, they dissociate 100% . They break up
into positive and negative ions in water
produced ions conduct an electrical current
Examples: KOH, HCl, HNO3, H2SO4...
Solutes that are weak electrolytes
Weak electrolytes
weak electrolyte
dissolve in water forming a few ions
produce solutions that conduct electricity weakly
Examples: HF, acetic acid, lactic acid, ammonia...
Nonelectrolytes
Solutes - nonelectrolytes are covalent compounds which:
nonelectrolyte
do not produce ions in water
form solutions that do not conduct an electrical current
Examples: sucrose, glucose, urea, ethanol, glycerol...
Average ion concentrations in blood plasma, ISF and ICF (mmol/L)
Electrolytes in body fluids
ICF – intracellular fluid
* Most of them are organic phosphates (hexose-P , creatine-P , nucleotides, nucleic acids)
ISF – interstitial fluid - the fluid in spaces between the tissue cells
Ionic composition of body fluids
Blood plasma and ISF (interstitial fluid) have almost identical
composition, ISF does not contain proteins
The main ions of blood plasma are Na+ and Cl-, responsible for
osmotic properties of ECF (extracellular fluid)
The main ions of ICF (intracellular fluid) are K+, organic
phosphates and proteins
Each body fluid is electroneutral total positive charge = total
negative charge
Interstitial
fluid
Water
Intracellular fluid ICF – inside cells – 25 - 30L
Extracellular fluid ECF – 15L - blood plasma, intersticial fluid,
lymph, fluid in gastrointestinal tract, urine...
Volume of water in body is balanced (intake = output in urine, feces,
sweating, lungs)
Central regulatory organ of water volume – kidneys
Hydrogen
bond
Water – H2O – a polar solvent
O
O
O
O
HH
H
H
H
H
H
H
Average total body water (TBW) as body weight percentage
The water content of the body changes with:
• gender
• age
• body composition (a lean person has a higher TBW than an obese person)
True solutions
Ionic Molecular
NaCl Na+ +
H2OCl
-• solutions of nonelectrolytes
• contain molecules of compounds in
solution (glucose in water, urea)
• solution of electrolytes in which ions
are present, formed by electrolytic
dissociation of ionic compounds
H2O
H2O
H2O
Hydrated
ions
Electrolytic
dissociation
H2O
Cl-
Cl-
Cl-
Cl-
Cl-
H2OH2O
Na+
Na+
Na+
Na+
Solubility
A measure of how much of a solute can be dissolved in a solvent
Saturated Solutions - contain the maximum concentration of a
solute dissolved in the solvent (under a given set of pressure and
temperature). Additional solute will not dissolve in a saturated
solution
Super Saturated Solutions contains more dissolved solute
than could ordinarily dissolve into the solvent. Undissolved
solid remains in the flask.
Unsaturated Solutions – a solution containing less than the
maximum concentration of solute that will dissolve under a given
set of conditions (more solute can dissolve).
Unsaturated Saturated
Super saturated
Factors affecting solubility
• Temperature
• Pressure
• Polarity
Solubility
Temperature
For most solids and most liquids
Solubility increases when solution temperature increases
Temperature
For gases
Higher temperature reduces solubility of gases –
it drives gases out of solution
Examples:
Carbonated soft drinks are more bubbly if stored in the
refrigerator (more CO2 is inside the drink)
Warm lakes have less O2 dissolved in them than cool lakes
Pressure
• little effect on solubility of solids and liquids
• will greatly increase solubility of gases
• Henry's Law: The solubility of a gas in a liquid is directly proportional
to the pressure of that gas above the surface of the solution.
Polar substances tend to dissolve in polar solvents.
Nonpolar substances tend to dissolve in nonpolar solvents.
Examples
Polarity
Vitamin A is soluble in nonpolar compounds (e.g. fats)
Vitamin C is soluble in water
Vitamin A Vitamin C
Properties of true solutions
Colligative properties don´t depend on the chemical composition of a
solute, but depend only on the number of solute particles (molecules or
ions).
The processes based on colligative properties are:
• Diffusion
• Dialysis
• Osmosis
• Freezing point depression
• Boiling point elevation
Diffusion
is a process of spontaneous movement of particles of a dissolved
compound from a region of higher concentration to a region of lower
concentration, to distribute themselves uniformly = movement of a
substance down a concentration gradient
The rate of diffusion depends on the concentration gradient
Particles move until equilibrium is reached
Diffusion usually happens in a solution in gas or in a liquid.
Examples of diffusion:
A sugar cube is left in a beaker of water for a while.
The smell of food spread in the whole house
Biomedical importance of diffusion
Exchange of O2 and CO2 in lungs and in tissues
Certain nutrients are absorbed by diffusion in the gastrointestinal
tract e.g. water soluble vitamins, minerals...
Dialysis
Water and low molecular weight (LMW) compounds (not macromolecules)
are transported across a semipermeable membrane. LMW compounds go from
the more concentrated solution to the less concentrated solution till equilibrium is
reached.
Concentrated
sugar solutionDiluted
sugar solution
Movement of LMW solute
to equal concentrations
Semipermeable membrane
Biomedical importance of dialysis
Biological ultrafiltrates
Many extracellular fluids like interstitial fluids, CSF, glomerular filtrate of
kidneys are formed by ultrafiltration. Proteins do not appear in ultrafiltrates.
Hemodialysis - Blood dialysis
- in patients with acute kidney injury blood is dialyzed in artificial
kidney to eliminate waste products (e.g. urea or creatinine) or toxins
Filtered blood
returning to body Blood flows to
dialyzer
Hemodialyzer
machine
Hemodialyzer
(where filtering takes place)
Biomedical importance of dialysis
Dialyzing
membrane
Dialysate
- solution isotonic with blood,
- it has the same concentrations of all the
essential substances that should be left in blood
Dialysate
Osmosis
Osmosis is the flow of solvent (e.g. water) across a semipermeable
membrane (with smaller pores than dialyzing membrane) from a
lower solute concentration to a higher solute concentration
semipermeable membrane is permeable only to solvent molecules,
not to solute molecules
Concentrated
solution
Diluted
solution
Semi-permeable
membrane
Osmotic pressure (π)
- external pressure that has to be applied on the more
concentrated solution to prevent osmosis
i – number of solute particles in solution to which the compound dissociates
c – amount of substance concentration (mol/L)
R – gas constant – 8.314 J K-1 mol-1
T – temperature in Kelvins (0 °C = -273.15 K)
π = i . c . R . T
π of blood - 780 kPa
Movement of solvent (water)
to equal concentrations
π
Osmolarity (cosm)
molar concentration of all osmotically active particles of solutes in
solution
cosm = i . c
cosm - osmolarity mol/L
i – number of solute particles in solution to which the
compound dissociates
c – amount of substance concentration (mol/L)
Osmolarity (cosm)
Blood serum osmolarity:
πblood = i . c . R . T
cosm
πblood
Blood cosm = = 0.3 mol/L R . T
• Osmolarity is kept constant by kidneys
.
= 780 kPa
Isotonic /isoosmotic solutions
Isotonic solutions are two solutions of equal osmolarity.
Hypertonic solution
Hypertonic solution is one of two solutions that has a higher
osmolarity.
Hypotonic solution
Hypotonic solution is one of two solutions that has a lower
osmolarity.
hemolysis
Crenation
Cells shrink
Solution of NaCl with concentration of 0.15 mol/L
Solution of NaCl with osmolarity of 0.3 mol/L
0.9% NaCl solution (9 g NaCl/L)
Physiological solution
Solution which osmotic pressure corresponds to blood plasma:
Any solution added in large quantity into the bloodstream has
to be isotonic with blood!!
Oncotic pressure
The capillary wall is permeable for small molecules and water but not
permeable for proteins
protein
Oncotic pressure
Oncotic pressure, or colloid osmotic pressure, is a form
of osmotic pressure exerted by proteins (e.g. albumin) in a blood
that usually tends to pull water into the circulatory system.
Water flow driven by
oncotic pressure
diference
Capilary
lumen
The significance of oncotic pressure
Small molecules and ions can be dialyzed in both directions between
blood and the interstitial compartment
Large protein molecules do not have this ability – their presence
produces excess osmotic pressure of blood (oncotic pressure)
compared to the interstitial fluid.
The hydrostatic pressure of the blood (at the arterial end of
capillary) tends to push water out of the capillary – filtration.
The oncotic pressure (at the venous end of capillary) pulls the
water from the interstitial space back into the capillary –
reabsorption.
Important function of oncotic pressure:to maintain water in capillaries
If capillaries become more permeable for proteins
(surgical procedures or extensive burns)
proteins migrate from blood
loss of blood oncotic pressure
total blood volume decreases
reduces the ability of blood to transfer oxygen and to eliminate CO2
Decrease of blood volume associated with insufficient brain oxygen supply
leads to shock
Biomedical importance of oncotic pressure
If plasma oncotic pressure is reduced (starvation, kidney disease)
Reduced force drawing water back into capillary from interstitium
Biomedical importance of oncotic pressure
Edema
Accumulation of excess fluid in tissue spaces
Colloidal dispersions
Colloidal dispersion
size of particles 1 – 1000 nm
almost all reactions in the organism proceed in colloid environment
True
solution
Colloid
High–molecular weight
(macromolecular) compounds
(e.g. proteins, polysaccharides)
Colloidal dispersion
Low–molecular weight compounds
by clustering of molecules into
aggregates – micelles
(e.g. soap solutions).
Classification of colloids
Colloids are classified based on the following criteria:
Physical state of dispersed phase and dispersion medium
Affinity of dispersed molecules with dispersing media
Classification of colloids
1. Based on physical state of dispersed phase and
dispersion medium
• Sol – colloids with solid particles dispersed in a liquid
• Emulsion - liquid dispersed in liquid (immiscible liquids)
• Foam – gas particles dispersed in a liquid or solid
• Aerosol - small liquid particles or solid dispersed in a gas
Sauces and dressingsclouds
• Gel - liquid particles dispersed in a solid
gelatin
Sols
Are colloidal solutions made of globular proteins with normal
viscosity
Sol - a colloidal solution appears as fluid
Gels
.
they arise by swelling macromolecular compounds (e.g.proteins) in
solvent – acceptation of water by solid polymers
are formed from fibrous proteins (gelatin from collagen), polysaccharides
(gels – dextran, sephadex).
Gels - a colloidal solution appears as solid
Gels undergo aging - particles coagulate, gel volume diminishes and
water is displaced
Emulsions
are colloidal dispersions of two immiscible liquids (e.g. oil in water, or
water in oil) when are shaken together.
usually are not stable (e.g. the oil soon separates from the aqueous layer).
can be stabilized by a third component called emulsifying agent
(emulsifiers).
Biologically important emulsifying agents are salts of bile acids.
Emulsifiers
Hydrophilic
water-loving head Hydrophobic
water-fearing tail
• All emulsifiers have 2 components: hydrophilic head
hydrophobic tail
• enable fat to be uniformly dispersed in water as an emulsion (they
stabilize emulsions).
• Their action is similar to soap in washing
emulsifier
Emulsifiers
Oil droplets
Hydrophilic head will associate with water and its hydrophobic tail with oil droplets.
This prevents separation of two layers and thus stabilizes the emulsion.
emulsifier emulsifier
Hydrophobic groups
(nonpolar)
Hydrophilic groups
(polar)
Bile acids as emulsifiers
Fat
Fat
Fat
Fat
Fat Fat
Step 1: Emulsification of fat droplets
Step 2: Hydrolysis of triacylglycerols in emulsified fat droplets into fatty acid and monoacylglycerols
Sterp 3: Dissolving of fatty acids and monoacylglycerols into micelles to produce „mixed micelles“
Bile acids as emulsifiers
Foam
is composed of small bubbles of gas (usally air) dispersed in a liquid (e.g.
egg white foam)
As liquid egg white is whisked, air bubbles are incorporated.
If egg white is heated, protein coagulates and moisture is driven off. This
forms a solid foam, e.g. a meringue
Colloids
LyophilicLiquid-loving
Lyophobic
Liquid-hatingMicelles
2. Classification of colloids according to the affinity
of dispersed molecules with dispersing media
Macromolecular
compounds Low-molecular
weight compounds
Low-molecular
weight amphipatic
compounds (soaps)
1. Lyophilic colloids
• If water is the solvent (dispersing medium), it is known as a
hydrosol or hydrophilic colloids
• particles of a lyophilic colloid are stabilized in solution
(prevention of aggregation) by solvation (hydration) shell, i.e.
oriented solvent molecules
• are formed by spontaneous dissolving of macromolecular substances
(e.g. solutions of proteins, starch...)
1. Lyophilic colloids
The loss of hydration shell after excess of neutral salt (electrolyte) is
added into solution results in irreversible salting out (precipitation)
of particles from solution.
The living cells represent solutions of lyophilic colloids (as well as
coarse dispersions)
• solvent hating colloids, have no affinity for the dispersion medium
2. Lyophobic colloids
• unstable colloid systems in which the dispersed particles:
- tend to repel liquids,
- are easily precipitated
• require protective colloids (lyophilic colloids – gums, gelatin...) to
stabilize in water
Lyophobic soll particle
(particle being protected)
Lyophilic colloidal particle
(protecting particle)
Explanation: The particles of the hydrophobic sol adsorb the particles
of the lyophilic particles. The hydrophobic colloid, therefore, behaves
as a hydrophilic sol and is precipitated less easily by electrolytes.
2. Lyophobic colloids
• are made artificially by aggregation of low molecular weight substances
• Examples: sols of metals and their insoluble compounds like sulphides and
oxides (e.g. gold, silver, platinum in water, cluster of inorganic molecules,
e.g. As2S3)
• Aplication in therapy: colloidal systems are used as therapeutic agents
Silver colloid – germicidal effects
Copper colloid – anticancer effects
Mercury colloid - antisyphilis
Colloidal gold
Colloidal silver
3. Association colloids – micelles
are formed by dissolving of low-molecular weight amphipathic compounds
Amphipathic compounds contain both polar (hydrophilic) and nonpolar
hydrophobic regions (e.g. fatty acids, phospholipids)
Polar part
Nonpolar part
when mixed with water, amphipatic compounds form colloidal particles –
micelles (e.g. soap, detergents)
Hydrophilic headHydrophobic tail
Biological importance of colloids
Biological compounds as colloidal particles: high-molecular weight proteins,
complex lipids and polysaccharides
Blood coagulation: when blood clotting occurs, the sol is converted finally
into the gel.
Biological fluids as colloids: these include blood, milk and cerebrospinal
fluid, lymph, mucus, cytosol, nucleus, cell membranes
Colloidal state is one of the most widespread in nature:
Reaction kinetics
Chemical reaction
Reaction means a change
Chemical reaction is a conversion of reactants to products
A + B C + DReactants Products
Reagents
Irreversible reactions
Reversible reactions
A + B C + D ReactantsProducts
Chemical kinetics
Kinetics of a chemical reaction can tell us:
how fast the concentration of A or B decreases
how fast the concentration of product C increases
A + B C
Rate equation(Guldberg Waage rate law)
The rate of a given chemical reaction (at constant temperature and
pressure) is proportional to product of reactants concentration.
Rate: v = k . [A]a . [B] b
k = rate constant
[A], [B]= molar concentrations of reactants (mol/L)
For the general reaction:
aA + bB cC
Rate constant
k = rate constant
A = Arrhenius constant for each chemical reaction (total number of collisions)
Ea = activation energy
R = gas constant (8.314 J K-1 mol-1)
T = Temperature in Kelvins
e = euler number (2.71828...)
Temperature has a dramatic effect on reaction rate.
For many reactions, an increase of 10°C will double the rate.
Effective collisions
For reactants to make products
They must collide in the correct orientation and with sufficient energy
The correct orientation of collisions
A B C D
A B A B
Effective collisions
For reactants to make products
They must collide in the correct orientation and with sufficient energy
The energy of collision must be greater than the bond energy
between the atoms
Activation energy
The minimum amount of energy required to start a chemical reaction
it is used to overcome the electrostatic repulsive forces between colliding
entities,
it is used to weaken the bonds of the reactants.
Activation energy
Activation energy
Transition state
(activated complex)
Activation energy
Reactants
Products
Factors which affect the rate of chemical
reactions
Rate of
reaction
The nature of
reactants
Temperature
Concentration
of reactants
Catalysts
Natu
reo
fre
acta
nts Number of bonds
• fewer bonds per reactant - faster reaction
Strength of bonds• Breaking of weaker bonds - a faster rate
(-C-C- / -C=C-)
The size and shape of a molecule• Complicated molecules or complex ions
are often less reactive
Less particles, less frequent
and successful collision
More particles, more frequent
and successful collision
Concentration of reactants
As the concentration of reactants increases, so does the likelihood that reactant
molecules will collide - the reaction rate will increase
A temperature increase of about 10°C will often double the rate of a reaction
Higher
temperatureHigher
speedMore high-energy
collisionsMore collisions
that break bonds
Faster
reaction
Temperature
Catalysts Catalysts speed up reactions by changing the mechanism of the reaction –
they reduce activation energy of reaction
Catalysts are not consumed during the course of the reaction
EaEa
Does a catalyst shift the location of the equilibrium position?
No! Catalysts do not affect the amounts of reactants and products present at
equilibrium, just the time it takes to establish equilibrium.
A catalyst speeds up the forward and reverse reactions exactly the same
Oxidation – reduction reactions
(redox reactions)
Oxidation – reduction reactions
(redox reactions)
Oxidation is the loss of electrons (or hydrogen), the species which loses
the electrons is oxidized, it becomes more positive
Reduction is the gain of electrons (hydrogen), the species which gains
electrons is reduced, becomes less positive.
Na0 → Na+ + 1e-
Cl20 + 2e- → 2Cl-
Oxidation and reduction reactions occur simultaneously
chemical reactions where one of the reactants is oxidized and one of the
reactants is reduced
Biological oxidation-reduction reactions
In biological systems, oxidation is often synonymous with dehydrogenation
Many enzymes that catalyze oxidation reactions are oxidoreductases, called
dehydrogenases.
O : H ratio1 : 6
O : H ratio1 : 4
O : H ratio1 : 2
More reduced compounds are richer in hydrogen
Oxidizing agent – oxidant - is the chemical species causing the
oxidation. This species is reduced and can also be called the
electron acceptor.
2Na0 + Cl20 2Na+Cl-
oxidant
Reducing agent – reductant- is the species causing the
reduction. This species is oxidized and can be called the electron
donor.
reductant
The number of electrons lost by the reductant must be equal to the
number of electrons gained by the oxidant.
e-
Electrons are transferred from one molecule (electron donor) to another
(electron acceptor) in one of four different ways:
1. Directly as electrons Fe2+ + Cu2+ Fe3+ + Cu+
2. As hydrogen atoms
H = H+ + 1e- AH2↔ A + 2 eˉ + 2 H+
AH2+ B ↔ A + BH2
Hydrogen/electron donor
Reduced
3. As a hydride ion (Hˉ), which has two electrons (H+ + 2e-)
This occurs in the case of NAD+-linked dehydrogenases
4. Through the direct combination with oxygen
R−CH3+ ½O2 R−CH2OH
Dismutation (disproportionation)
The special case of oxidation – reduction reaction
a compound of intermediate oxidation state converts to two different
compounds, one of higher and one of lower oxidation states.
Examples:
The dismutation of superoxide free radical to hydrogen peroxide and oxygen,
catalysed in living systems by the enzyme superoxide dismutase
2O2. − + 2H+ → H2O2 + O2
With oxidation numbers:
2 O2. −1 + 2 H+1 → H2
+1 O2-2 + O2
0
SOD
Oxidation-reduction reactions
Oxidation – reduction reactions occur together
Fe2+ + Cu2+ Fe3+ + Cu+
This reaction can be described in two half-reactions:
(1) Fe2+ Fe3+ + 1e-
(2) Cu2+ + 1e- Cu+
Which ion is a reducing agent (reductant)?
Reductant – donates electrons
Which ion is an oxidizing agent (oxidant)?
Oxidant – accepts electrons
Electron donor e- + electron acceptor
Conjugate redox pair
Reduction potentials
When two conjugate redox pairs are together in solution, electron transfer from the electron donor of one pair to the electron acceptor of the other may occur spontaneously.
The tendency for a reaction depends on the relative affinity of the electron
acceptor of each redox pair for electrons.
The standard reduction potential (E0) is the tendency for a chemical
species to be reduced, and is measured in volts at standard conditions
H+ + eˉ ½ H2 E0 = 0 V
The electrode at which this half-reaction occurs is arbitrarily assigned a
standard reduction potential of 0.00V.
Fe2+ + Cu2+ Fe3+ + Cu+
Element with the more positive redox potential has a higher
affinity towards electrons – it has an oxidizing property
Element with the more negative redox potential has a lower
affinity towards electrons – it can easily donate electrons – it has
an reducing property
R is gas constant (8.314 JKˉ1molˉ1
T is temperature (in Kelvins)
n is the number of electrons transferred per molecule
F is the Faraday constant (9.68 . 104 Cmolˉ1).
The Nerst – Peterson equation:
The reduction potential of a half-cell depends on:
the chemical species present
on their concentrations
Reduction potentials in medicine
Known oxidation-reduction potentials of biological redox systems allow to
determine the direction and sequence of oxidation-reduction reactions in
biological systems.
The strict sequence of enzymatic reactions in “respiratory chain” allows a
gradual release of energy during biological oxidation.
Electron transport chain
Thank you for your attention...