Separation and Purification

There is no theoritical basis for separation

There are only models Empirical + chemical kinetic/chemical thermodynamic

Goal : To obtain pure material

To isolate components of a chemical mixture- then qualitative or quantitative analysis

Chemical Equilibrium SEPARATION Physical

More dominant

Non equilibrium

EQUILIBRIUM
Chemical equilibrium: Mass + length Underlying properties of molecule Interaction each other Occurs between two phase A sealed half-full bottle of gin contains a liquid which is ~40% EtOH and ~60% water. The vapor phase consists more EtOH than water Physical equilibrium: Mass + length Center of gravity

Thermodynamic: value of equilibrium constant and its temperature

Physical separation methods : Majority are not considere with equilibrium Examples: Ordinary centrifugation Ultracentrifugation in a salt gradient Filtration: the use of sand as a filtration medium; the use of pan to separate gold dust from silica sand by gold miners.it is separation method based on density Chiral separation Enantiomer can be divided 2 types: have physical properties differences or have the same of physical and chemical properties

Chemical separation methods :

Most, but not all chemical separation are based on equilibrium SOLUBILITY involved chemical interaction PRECIPITATION and FILTRATION just physical separation

Distillation and Extraction :

Based on: equilibrium and differences of equilibrium constant Distillation: a process in which a liquid or vapor mixture of two or more substances is separated into its component fractions of desired purity, by the application and removal of heat Physical separation not chemical separation Early forms of distillation were batch processes using one vaporization and one condensation Gas-Liquid interface, liquid from condensator returns to the pot and contacts with vapor rising from pot Extraction: Liqui-liquid interface The equilibrium is established by motion of solute molecules across the interface between the immiscible layers

Distillation:
depends on: the differences in boiling points of the individual components the concentrations of the components present the vapour pressure of a liquid at a particular temperature. The vapor pressure is the equilibrium pressure exerted by molecules leaving and entering the liquid surface Types of distillation include simple distillation, fractional distillation (different volatile 'fractions' are collected as they are produced), and destructive distillation (usually, a material is heated so that it decomposes into compounds for collection).

System consists of : Benzene (b.p. 80C) and Toluen (b.p. 110,6C)

Distillation:
Boiling point diagram. The boiling point of A is that at which the mole fraction of A is 1. The boiling point of B is that at which the mole fraction of A is 0. In this example, A is the more volatile component and therefore has a lower boiling point than B. The upper curve in the diagram is called the dew-point curve while the lower one is called the bubble-point curve. The dew-point is the temperature at which the saturated vapour starts to condense. The bubble-point is the temperature at which the liquid starts to boil. The region above the dew-point curve shows the equilibrium composition of the superheated vapour while the region below the bubble-point curve shows the equilibrium composition of the subcooled liquid.

Distillation:
For example, when a subcooled liquid with mole fraction of A=0.4 (point A) is heated, its concentration remains constant until it reaches the bubble-point (point B), when it starts to boil. The vapours evolved during the boiling has the equilibrium composition given by point C, approximately 0.8 mole fraction A. This is approximately 50% richer in A than the original liquid.

Distillation:
Relative volatility is a measure of the differences in volatility between 2 components, and hence their boiling points. It indicates how easy or difficult a particular separation will be. The relative volatility of component i with respect to component j is defined as

ij = [Yi/Xi]/[Yj/Xj]
yi = mole fraction of component i in the vapour xi = mole fraction of component i in the liquid Thus if the relative volatility between 2 components is very close to one, it is an indication that they have very similar vapour pressure characteristics. This means that they have very similar boiling points and therefore, it will be difficult to separate the two components via distillation.

Distillation:
VAPOR LIQUID EQUILIBRIUM (VLE) The VLE plot expresses the bubble-point and the dew-point of a binary mixture at constant pressure. The curved line is called the equilibrium line and describes the compositions of the liquid and vapour in equilibrium at some fixed pressure. VLE plot: ideal system (easily to be separated) and non ideal system (difficult to be separated)

Distillation:
AZEOTROPE An azeotrope is a liquid mixture which when vaporised, produces the same composition as the liquid. There are two models: with a maximum boiling point and with a minimum boilling point. In both plots, the equilibrium curves cross the diagonal lines, and this are azeotropic points where the azeotropes occur. Separation methods: Using 2 columns that operated at different pressure..composition azeotropic will be changed Adding a mass separation agent (known as an entrainer or solvent).change relative volatility

Distillation:
REFLUX Physically, what this means is that more and more liquid that is rich in the more volatile components are being recycled back into the column. Separation then becomes better and thus less trays are needed to achieve the same degree of separation. Minimum trays are required under total reflux conditions, i.e. there is no withdrawal of distillate Adverse vapour flow conditions can cause Foaming, Foaming refers to the expansion of liquid due to passage of vapour or gas. Although it provides high interfacial liquid-vapour contact, excessive foaming often leads to liquid buildup on trays Entrainment. Entrainment refers to the liquid carried by vapour up to the tray above and is again caused by high vapour flow rates weeping/dumping. This phenomenon is caused by low vapour flow. The pressure exerted by the vapour is insufficient to hold up the liquid on the tray Flooding. Flooding is brought about by excessive vapour flow, causing liquid to be entrained in the vapour up the column. The increased pressure from excessive vapour also backs up the liquid in the downcomer, causing an increase in liquid holdup on the plate above

Distillation:
Efficiency of separation Depends on: Column diameter If the column diameter is not sized properly, the column will not perform well Number of trays Weather Most distillation columns are open to the atmosphere. Although many of the columns are insulated, changing weather conditions can still affect column operation. Thus the reboiler must be appropriately sized

Distillation:
Basic equipment and process of distillation The vapour moves up the column, and as it exits the top of the unit, it is cooled by a condenser. The condensed liquid is stored in a holding vessel known as the reflux drum. Some of this liquid is recycled back to the top of the column and this is called the reflux. The condensed liquid that is removed from the system is known as the distillate or top product. Thus, there are internal flows of vapour and liquid within the column as well as external flows of feeds and product streams, into and out of the column.

Extraction
Definition: The distribution of a compound between 2 immiscible phase Extraction Process: Moving one or more compounds from one phase to another Based on a drive towards equilibrium Mass transfer Reasons: Isolation for characterization materials Purify compounds If the distillation is impossible because the relative volatility as more than 1.2; too expensive

Physical properties information (analytes and interfering compounds)

Structure (including functional group arrangement) Molecular mass Polarity Solubility pKa

Extraction
Classified according to a number of schemes: analytical versus preparative (depending on the quantity of pure compound to be separated) batch versus continuous (depending on the mode of feeding the material to be separated into the extraction apparatus); based on the physical principles involved (is the extraction strictly based on partitioning, or are adsorption or other processes involved?); based on the types of phases involved (so called liquidliquid extraction, gas-solid extraction, supercritical fluid extraction, etc.).

Extraction process
a series of steps:

Phase contact and equilibrium the extracting phase is brought into intimate contact with the sample phase (a diffusion process). the compound of interest partitions into the extracting phase liquid samples : this step is generally not problematic. solid samples: the compounds affinity for the extracting solvent must be greater than its affinity for the sample.
Phase separation the extracting phase (containing the compound of interest) must be able to diffuse back through the sample, separate into a distinct phase, and be removed for subsequent processing.

proper selection of the extracting solvent

External Work to increase the extraction capacity:

Heat .faster kinetics; decrease viscosity; decrease surface tension; increase solubility and diffusion Shaking

Selected extraction techniques by phases involved and the basis for separation

Solvent Considerations
Selectivity, can be supplemented by + adsorbents and secondary solvents, High distribution coefficient to minimize the solvent-sample ratio Solute solubility..usually related to polarity Ability to recover the extracted material..(emulsion and other deleterious must be minimized) High Capacity Density, the solvent density is related to solubility in supercritical fluid extractingsolvents.

Low interfacial tension to facilitate mass transferacross the phase boundary. Low relative toxicity. Nonreactive. In some instances, such as ionexchange extractions, known reactivity in the extracting fluid is used. Stable. Inexpensive.

Solubility
Solvent classification by snyder into 8 classes according to proton donor, proton acceptor and dipole interaction Relative solubility..hildebrand solubility (): = (Ev)/(V1/2) Ev = the heat (Energy) of vaporization necessary for volume V = interaction energy of the solvent-soulte is related to :
Hydrogen bonding ability (H) Dispersion coefficient (L) Polarity (p)

2 = (H)2 + (L)2 + (p)2 For extraction: it is preferable to use solvent that has value similar to that of solute solute = solvent

Other Solvent Classification

Class 1 solvents : capable of forming three dimensional networks of strong hydrogen bonds Class 2 solvents : have active hydrogen atoms and donor atoms but do not form three dimensional networks Class 3 solvents : contain donor atoms, but not active hydrogen atoms Class 4 solvents : contain active hydrogen atoms, but not donor atoms Class 5 solvents : do not have hydrogen-bonding capability or donor atoms

Solvent removal methods

Evaporation Distillation Precipitation Adsorption Back extraction Ex. Adjusting pH to change molecule or ionic form of solute

Ion Exchange Extraction

The ion compound is covalently bonded to a compound of opposite chargeresulting neutral species

Ion Pairing Extraction

Formation of a neutral ion pair through the interaction of the ionic species of solute with a counter ion. The resulting neutral compound is soluble in organic solvent. Counter ion used a generally soft acids or bases possesing large ionic radii

Ion Exchange Extraction

Cationic exchange X+ + R-K+ Anionic exchange X- + R+ClX+R- + K+ X-R+ + Cl-

Here, when an ion is transferred from the aqueous phase to the organic phase, another ion is transferred in the other direction to maintain the charge balance.

Ion Pairing Extraction

Ex. If the nitrate concentration is high, it is possible to extract as an anionic nitrate complex if the mixture contains a lipophilic quaternary ammonium salt

Solute Distribution
KD = [Solute in phase 1]/[Solute in phase 2] KD = [Solute in organic phase]/[Solute in aqueous phase]
KD cannot be determined from solubility:
Extraction may not be at equilibrium Mutual solubility of the phases Solubility differences for ex. Hydrated and anhydrous form KD can not be determined from the ratio of solubility

Diffusion
The important factor influencing the extraction Spontaneous and Irreversiblesolutes moves from an area of high concentration to an area of low concentration, resulting in a concentration equilibrium within a single phase

Diffusion

Diffusion in solid

Diffusion in liquid

Diffusion in solid is also influenced by the geometry or tortuosity of pore structure

KD = [Solute in solid]/[Solute in solvent]

Extraction Techniques:

Liquid-Liquid extraction Solid phase Extraction.also for sample enrichment Leaching Soxhlet Extraction Sonication Ultrasonic energy is applied to disrupt solute-sample interaction and facilitate solute dispersion Accelerated solven extraction.by giving pressure Microwave assisted extraction Supercritical Fluid Extraction Ex. Using CO2 at temperature and pressure near or above the critical point..gas-like diffusion and liquid-like solvation properties Rapidso deleterius effect can be minimized Gas Phase Methods

sample/solvent

solvent/sample

Supercritical fluid extraction: Supercritical fluid: gas-like diffusion liquid-like solvation properties do not surface tension Relative more rapid Deleterious effect can be minimized Solvating properties can be modified as a function of temperature and pressure

CRYSTALLIZATION
Crystallization: Separation technique where a solid phase is separated from a mother liquor Occurs when supersaturation is created that acts as the driving force for crystallization SOLUBILITYis a key factor The kind of crystallization: Evaporative crystallization Cooling crystallization Precipitation crystallization Melt crystallization Supercritical crystallization

CRYSTALLIZATION.

CRYSTALLIZATION
Precipitation Crystallization: The drop-out of solid phase is achieved by mixing two stream that are either two reactans or a solvent containing the solute and antisolvent
Melt Crystallization: Melt crystallization differs from other crystallization methods in the fact that the operating temperature is close to the melting temperature of the main component. The advantages of melt crystallization are in the relatively low energy demand of the freezing process and in the high selectivity of crystallization

CRYSTALLIZATION.

CRYSTALLIZATION.

CRYSTALLIZATION PROCESS

Influences:
Particle size Crystal shape Degree of agglomeration Caking behaviour Purity

CYCLICAL DSC Formation of metastable acetaminophen:

Acetaminophen

Wax
Heated at 80 5 C

Suspension of Acetaminophen in wax

Allowed to cool Filtration

Spray the atomized onto cooled air

CRYSTAL (1) CRYSTAL (2) FILTRATE

Heated at 100-110C Cooled

CRYSTAL (3)

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CYCLICAL DSC Formation of metastable acetaminophen:

The melting point shifted approximately 10C

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