Details of Buffe s fering Sys stem

Ability o a buffer solution to resist changes in pH is result of equilib of o H t brium betw ween a weak acid + (HA) & i conjuga base (A ): HA(aq) + H2O(l) H3O (aq) + A (a its ate aq) Any alkali added to solution i consumed by hydro o is d onium ions.. These ion are most regenera as ns tly ated equilibriu moves to right & some of a dissoci um acid iates into h hydronium ions & con njugate bas If a se. strong ac is adde conjuga base is protonated & pH is almost en cid ed, ate d, s ntirely rest tored. This is an s example of Le Cha atelier's prin nciple & co ommon ion effect. Th contras with sol n his sts lutions of strong acids or s strong base where an addition strong a or base can great change p This m be es, ny nal acid e tly pH. may easier to see by com mparing two graphs: W o When a stro acid is t ong titrated wit a strong base, curve has a th e large gra adient thro oughout, sh howing tha a small addition of base/a at l acid has a large effe by ect; comparis a weak acid/stron base titr son, k ng ration curve has a sma gradien when pH is close to pKa e aller nt H t value.

Titra ation of a w acid w a stron base; the flat region at pKa is buffering r weak with ng e n region. Titra ation of a s strong acid with a stro base; note sharp r in pH t cannot buffer. ong rise this

When w writing abou buffer sy ut ystems, the can be r ey represented as combin d nation of a weak acid with d salt of its conjugate base, or co s ombination of a weak base with salt of its c n conjugate acid.

Calculat pH v ting values

Equilibrium reaction noted ab has fol bove llowing acid dissociati constan d ion nt: manipulation with loga arithms giv Henders ves son-Hassel lbalch equa ation, descr ribes pH in terms n Simple m of pKa: quation, In this eq [A is conc A] centration of conjuga base & is conside ate ered as com ming comp pletely from salt, m since acid supplies relative few anio compar to salt. e ely ons red [H is con HA] ncentration of acid & is conside ered as com comp ming pletely from acid, sinc salt m ce + supp relative few com plies ely mplete acid molecules (A may e d extract H f from water to become HA) r e comp pared to ad dded acid. M Maximum b buffering c capacity is obtained when pH = pKa, & buffer range is usually H u considered to b for pH = pKa 1. be .

Illustrat of bu tion uffering ef ffect: Sodi acetat ium te/acetic acid

Acid diss sociation co onstant for acetic acid d-sodium ac cetate is giv by equa ven ation:
Mechanism of Buffering System-Comp by M. Rez Karim Tut m piled zaul tul

Since this equilibriu only inv um volves a we acid & base, it can be assum that ion eak n med nization of acetic f acid & h hydrolysis o acetate i of ions are ne egligible. In a buffer c n consisting of equal am mounts of acetic f acid & so odium aceta equilibr ate, rium equat simplif to tion fies + Ka = [H ], & pH of buf as is eq to pKa. ffer qual To deter rmine effec of addition of a strong aci such as HCl, foll ct id lowing mat thematics would provide n pH. S new Since HCl is a strong acid, it is compl l t letely ioniz in solu zed ution, incr reasing + concentra ation of H in solutio which th neutral on, hen lizes acetate by follow equatio e wing on. Consume hydrogen ions chan effectiv number o moles of acetic acid & acetate ions: ed nge ve of f d e After acc counting fo volume c or change to determine c d concentratio new pH could be calculated from ons, H e d Henderso on-Hasselb balch equat tion. Any neutralizatio results i a small c n on in change in p since it is on pH, t a logarith hmic scale.

Applications
Given the resistance to chang in pH, buffer solu eir ges utions are v useful f chemical manufac very for cturing & essenti for man biochemical processes. Ideal b ial ny buffer for a particular pH has a pKa equal to pH desired, s since a solu ution of thi buffer would conta equal am is ain mounts of acid & base & be in middle e m of range of bufferin capacity Buffer so ng y. olutions ar necessary to keep c re y correct pH for enzym in H mes many org ganisms to work. Man enzymes work only under ver precise c ny s y ry conditions; if pH stra too ays far out o margin, enzymes sl or stop working & can den of low p nature, thus permanen disabli its ntly ing catalytic activity. A buffer of carbonic a (H2CO3) & bicar acid O rbonate (H 3 ) is present in blood HCO plasma, to maintai a pH between 7 in 7.35 & 7.4 Indust 45. trially, buf ffer solutio are us in ons sed fermentat proces & in se tion sses etting appro opriate con nditions for fabric pro r ocessing. They are also used T o in chemic analyses syntheses & for cali cal s, s, ibration of pH meters f s.

Bufferin agents ng
A bufferi agent a ing adjusts pH of an acid or alkali solution & stabiliz it at th pH. Buf dic ine n zes hat ffering agents ha variable properties some are acidic, oth are basic; some ar more sol ave e s: hers re luble than o others. They are useful for a variety of applica e r ations, inclu uding agric culture, foo processing, medicine, & od photogra aphy. Buffe ering agents & buffer solutions are similar in that th both regulate pH of a s r r hey r H solution & resist ch hanges in pH They fu H. unction bas on sam chemical principles & however, may sed me be disting guished by following differences s: A buffer so olution mai intains pH of a syst H tem, preventing large changes in it, whe e ereas a buffe fering agent modifies p of what it is place into. t pH t ed A buffering a agent is the active com e mponent of a buffer solution. f

Example es

Buffe fered aspirin has a buf n ffering agen such as magnesium oxide, th maintain pH of a nt, m hat ns aspirin

as it passes thro ough patien stomach nts h. Buffe fering agent are also present in a ts p antacid tabl are use mainly t lower aci lets, ed to idity in stom mach.
Mechanism of Buffering System-Comp by M. Rez Karim Tut m piled zaul tul

 Mono-potassium phosphate (MKP) is a buffering agent with a mildly acidic reaction. When

used as a fertilizer component with urea or di-ammonium phosphate, it minimizes pH fluctuations that can cause loss of nitrogen.

Common buffer compounds used in biology

Common Name TAPS Bicine Tris Tricine HEPES TES MOPS PIPES Cacodylate MES Acetate pKa at Buffer 25C Range 8.43 8.35 8.06 8.05 7.48 7.40 7.20 6.76 6.27 6.15 4.76 7.7-9.1 7.6-9.0 7.5-9.0 7.4-8.8 6.8-8.2 6.8-8.2 6.5-7.9 6.1-7.5 5.0-7.4 6.1-7.5 3.8-5.8 0.011 Temp Effect Mol. Full Compound Name (pH / C)** Weight 0.018 0.018 0.028 0.021 0.014 0.020 0.015 0.008 243.3 3{[tris(hydroxymethyl)methyl]amino}propanesulfonic acid 163.2 N,N-bis(2-hydroxyethyl)glycine 121.14 tris(hydroxymethyl)methylamine 179.2 N-tris(hydroxymethyl)methylglycine 238.3 4-2-hydroxyethyl-1-piperazineethane sulfonic acid 229.20 2{[tris(hydroxymethyl)methyl]amino}ethane sulfonic acid 209.3 3-(N-morpholino)propane sulfonic acid 302.4 piperazine-N,N-bis(2-ethanes ulfonic acid) 138.0 dimethylarsinic acid 195.2 2-(N-morpholino)ethane sulfonic acid 59.04

** Values are approximate

Making buffer solutions

In general, preparing a buffer solution requires either: A weak acid & a salt of acid's conjugate base. Or a weak base & a salt of base's conjugate acid. Both of which in sufficient amounts to maintain ability to buffer

Example: Citric acid-phosphate buffer

Make 0.1M citric acid & 0.2M Disodium hydrogen phosphate solutions-mix as below to make a 100ml solution: Citric acid-phosphate buffers pH 0.2M Na2HPO4 0.1M Citric 3.0 20.55 ml 79.45 ml 4.0 38.55 ml 61.45 ml 5.0 51.50 ml 48.50 ml 6.0 63.15 ml 36.85 ml 7.0 82.35 ml 17.65 ml 8.0 97.25 ml 2.75 ml

Background of Invention
This invention relates to use of liquid ingredients to provide a pH setting &/or buffering system that is beneficial to preparation, treating, dyeing, printing & finishing of textile materials such as
Mechanism of Buffering System-Compiled by M. Rezaul Karim Tutul

fibre, yarn, fabric & carpet. Invention also has utility in non-textile industrial operations where processing in water systems occurs, as a replacement & improvement for solid phosphate pH setting &/or buffer ingredients. For proper treatment in dyeing & finishing of textile materials, it is practice to select a pH range that is best suited to particular operation. These operations can be carried out in water at various temperatures or by application of water suspended or dissolved ingredients directly onto material. pH is a term used to express a measure of acidity or alkalinity & if it fluctuates widely & if not controlled can cause erratic results. To control pH fluctuations, chemicals are added to liquid treating bath. Such chemicals used to set or control pH fluctuations are called buffers. Preparation, treating, dyeing, printing & finishing of textile material such as fibre, yarn, fabric, & carpet involves placing textile material into a vessel containing water & various compounds dispersed, dissolved, emulsified, or suspended in water for purpose of creating desired effects on textile material. This water based mixture is called bath. Specific process may require a short term immersion in bath, such as a padding operation in finishing or preparation area. In this case, material is run continuously through a trough containing bath with a dwell time of only a few seconds. Material is then often squeezed dry by means of nip rolls. In other cases, material is left immersed in bath for long periods of time (up to 12 hours) to allow chemicals in bath to act on textile substrate. Various conditions of temperature, acidity, alkalinity, etc. may be used to produce desired effects on material. Some examples of typical chemicals which may be contained in a textile bath are listed below:

Preparation:
surfactants Finishing: resin finish hydrogen peroxide hand builder sodium hydroxide softener silicate lubricant stabilizers pH control pH neutralizers agents (buffers) (buffers) Printing: acrylic polymers thickeners pH control agents (buffers) dyestuffs or pigments surfactants oils softeners Dyeing: surfactant solvent swelling agents pH control agents (buffers) salt softener lubricants Dyestuffs Thickeners Defoamers. Among commonly used materials for buffering &/or setting pH are Monosodium Phosphate (MSP), Disodium Phosphate (DSP), & Tri-sodium Phosphate (TSP). These materials are solids, & users have been faced with difficulties in measuring, handling & dissolving of these materials. For example, these solid products are commonly packaged in 50/100lbs bags. These bags must be manually lifted & opened, a procedure that often results in strained muscles, spill waste from broken bags, & poor control over material usage. These powders must then be diluted in a premixing tank before being fed into textile processing equipment. This is a time consuming operation, & unless employees involved in powder dilution are very conscientious, lumps of undissolved product may flow into equipment or drain lines can clog with solid particles. These difficulties associated with handling solid phosphates-spillage, lost time from physical strain, disposal or empty bags, time spent in dividing operating difficulties because of incomplete dissolved solids-are of great concern & have been a long-standing problem in dye house operations.

Summary of Invention
Mechanism of Buffering System-Compiled by M. Rezaul Karim Tutul

It is discovered that above noted prior art problems with respect to solid phosphate buffers can be eliminated by use of liquid buffer ingredients are easy to handle & measure, & mix readily with water. Liquid buffer system of present invention is designed to use a low pH liquid buffer ingredient & a high pH liquid buffer ingredient either alone or a combination of two that provides a pH & buffering action in a preselected range, ranging from high pH to low pH, desired preselected pH range being considered optimum for particular processing operation. High pH liquid buffer ingredient performs in range where solid TSP (Trisodium Phosphate) is used. Low pH liquid buffer ingredient performs in range where solid MSP (Monosodium Phosphate) is used. By a combination of high pH liquid ingredient & low pH liquid ingredient, pH range of DSP (Disodium Phosphate) can be covered. Thus use of high pH buffer ingredient & low pH buffer ingredient serves to cover full range that can be covered by solid sodium phosphate buffers. Monosodium phosphate (also sodium phosphate, monobasic) is highly soluble in water even at low temperatures and can be used as an ingredient for a low pH liquid buffer ingredient. Tri-sodium phosphate however is not soluble enough to be considered a suitable ingredient for a high pH liquid buffer ingredient particularly for cold temperature storage. However, tri potassium phosphate (also potassium phosphate, tribasic) has good solubility in water and is a suitable ingredient for a high pH liquid buffer ingredient. By a combination of these two ingredients, a system has been developed for using liquid buffer mixes in place of solid phosphate buffers. In carrying out present invention, it is important to make high pH & low pH liquid buffer ingredients with high concentration in order to achieve product economy versus solid phosphate buffer ingredients. Discovery of suitability of tri-potassium phosphate as a high pH buffer ingredient for its high solubility in water is critical to practicality of invention. High concentration of high pH liquid buffer ingredient would not be possible using tri sodium phosphate, usual solid high pH buffer ingredient.

Detailed Description of Invention

Liquid buffer ingredients of present invention can be formulated over a wide concentration range. For reasons of economy in preparation storage & shipping, concentration of tri potassium phosphate is usually at least about 20-50% by weight in water. Concentration of monosodium phosphate is from about 13-40% by weight in water. Liquid buffer ingredients can be constituted to provide for formation of additional buffering chemicals in situ, by incorporating chemicals in two liquid buffer ingredients that reacts chemically on mixing to provide additional buffering material in solution. High pH liquid buffer ingredient can be formulated to contain free Potassium Hydroxide in addition to tri potassium phosphate. Small amounts of sodium hydroxide may be added to enhance temperature stability of high pH liquid buffer ingredient. Low pH liquid buffer ingredient can be formulated to contain free phosphoric acid in addition to monosodium phosphate. When high pH liquid buffer ingredient is mixed with low pH liquid buffer ingredient, free potassium hydroxide & free phosphoric acid reacts to form a potassium phosphate which would be a buffer formed in-situ. This would reinforce buffering action of tri potassium phosphate which was in high pH liquid buffer ingredient, & monosodium phosphate that was in low pH liquid buffer ingredient. Reaction of this free phosphoric acid & free potassium hydroxide could be represented as an example by the following:
Mechanism of Buffering System-Compiled by M. Rezaul Karim Tutul

KOH+H3 PO4.....KH2 PO4 +H2O+2KOH+H3 PO4 ......K2 HPO4 +2H2O+3KOH +H3 PO4.....K3 PO4 +3H2 O Any free NaOH present would react in a similar way to form comparable Na3 PO4 in addition to K3 PO4. Solid phosphates of prior art give inferior buffering in pH range of about 8-10. When desired, liquid buffer ingredients can be modified by addition of borax &/or ethanolamines to improve buffering of system in range of about 8-10. When used with low pH buffer composition or ingredient, concentration of phosphoric acid should be in range of about 0-30% by weight, while monoethanolamine, diethanolamine, or triethanolamine alone or in combination should be in range of about 1.9-4% by weight. When used with high pH buffer composition or ingredient, concentration of borax pentahydrate should be ranging of 4-10% by weight. Monoethanolamine, diethanolamine, or triethanolamine alone or in combination should be in range of about 4-8% by weight. Potassium hydroxide should be in range of about 2.5-20% weight with a preferred range of about 4-9% being used in certain applications. Sodium hydroxide, when used, should be in range of about 0.4-7% by weight. Liquid buffers of present invention are added in range of about 0.1-0.3% by weight of dye bath. This range is on as is basis & is total for sum of low pH & high pH liquid buffers. This range applies for dyes other than fibre reactive dyes in which liquid buffers are added in range of about 0.25-1.5% by weight of dye bath. Concentration of dyes in dye bath ranges about 0.1-1% by weight. Salt ranges from about 0-10% by weight. Levelers & surfactants range from about 0-0.3%. Sequestering agents range from 00.05%. All percentages are by weight of dye bath. A typical method which may be used for making low pH liquid buffer is as follows: Into a mixer add 55.0 parts water & stir. Then add 31.0 parts sodium phosphate, monobasic (MSP) & stir until dissolved. Then add 14.0 parts phosphoric acid. Stir until uniform & then transfer material to a suitable container. High pH liquid buffer can be made as follows: Into a mixer add 56.6 parts water & stir. Then add 31.6 parts potassium phosphate tri-basic (TKP) & stir to dissolve. Then add 7.9 parts potassium hydroxide & stir to dissolve. Add 3.9 parts sodium hydroxide & stir to dissolve. Cool & transfer to a suitable container. Chemicals used are corrosive & should be handled with proper precaution & with proper safety equipment. Typical examples of seven formulations of present invention found suitable for low pH liquid buffer ingredients & for high pH liquid buffer ingredients are tabulated below in parts by weight: 1. Low pH Liquid Buffer Ingredient Sodium Phosphate, Monobasic 15.3 parts Water 56.5 parts Monoethanolamine 1.9 parts Phosphoric Acid 26.3 parts 2. Low pH Liquid Buffer Ingredient Sodium Phosphate, Monobasic 31.0 parts Phosphoric Acid 14.0 parts Water
Mechanism of Buffering System-Compiled by M. Rezaul Karim Tutul

55.0 parts 3. High pH Liquid Buffer Ingredient Potassium Phosphate, Tribasic 42.9 parts Water 57.1 parts 4. High pH Liquid Buffer Ingredient Potassium Phosphate, Tribasic 30.1 parts Borax Pentahydrate 4.0 parts Triethanolamine 7.1 parts Water 58.8 parts 5. High pH Liquid Buffer Ingredient Potassium Phosphate, Tribasic 21.4 parts KOH 2.9 parts Borax Pentahydrate 8.4 parts Triethanolamine 6.2 parts Water 61.1 parts 6. High pH Liquid Buffer Ingredient, Potassium Phosphate, Tribasic 29.2 parts KOH 12.3 parts Water 58.5 parts 7. High pH Liquid Buffer Ingredient Potassium Phosphate, Tribasic 31.6 parts KOH 7.9 parts Sodium Hydroxide 3.9 parts Water 56.6 parts. A high pH liquid buffer ingredient may be used alone with certain fibre reactive dyes for dyeing of rayon & cotton as a replacement for TSP (trisodium phosphate). In reactive dyeing of cellulosic textile materials, an alkaline material is needed to provide conditions that promote formation of a chemical bond between the reactive dye & cellulosic textile material. The firm chemical bond between dye & cellulosic textile material is responsible for excellent wash fastness produced on cellulosics with reactive dyes. Commonly used alkaline materials include NaOH, trisodium phosphate (TSP), sodium silicate, sodium carbonate, & sodium bicarbonate. A high pH liquid buffer may be used as a replacement for commonly used alkaline material in reactive dyeing of cellulosic textile materials (e.g. rayon, cotton, flax) & blends of cellulosic textile materials with other natural or synthetic textile materials. High pH liquid buffer performs comparably with commonly used alkaline materials in creating necessary reaction conditions & in producing level full shade dyeings. In addition, less of high pH liquid buffer on a weight basis is needed to do same job as optimum amount of commonly used alkaline material. Following example illustrates an application of use of a high pH liquid buffer in a reactive dyeing operation.

Example I
Into a suitable dyeing beaker containing an agitator, 5gm of bleached 100% cotton fabric, are placed in a bath of 125ml water, 6.25gm of common salt, & 0.2gm Remazol Red 3FB dye. Bath is stirred for 15mins, warmed to 104 F & held for 15mins. Then 1.25gm of high pH liquid buffer ingredient No. 6 are added to bath. Bath is heated to 140 F & held for one hour & then allowed to cool to room temperature. Cotton is removed from bath & washed thoroughly. The use of 1.25gm of liquid buffer No. 6 in this procedure results in a dyeing of equal shade depth & fastness properties as compared with using 2.50gm of TSP as high pH buffer in same procedure. High pH liquid buffer ingredient & low pH liquid buffer ingredient may be used together to set & hold a pH level between about 5.0-9.0 for a dyeing operation. Following example illustrates an application of two buffer ingredients in a typical dyeing operation.

Example II
Into a suitable dyeing beaker containing an agitator, 10gm of nylon 6 tufted carpet are placed in a bath of 150ml water. 0.1gm levelling agent, 0.01gm Nylosan Red F2R & 0.01gm low pH liquid buffer ingredient No. 1 plus 0.14gm high pH liquid buffer ingredient No. 5 to control pH in range of about 8.3-8.6. Use of low pH liquid buffer ingredient No. 1 & high pH liquid buffer ingredient No. 5 in this way produces a dyed carpet of similar colour yield & appearance to dyeing
Mechanism of Buffering System-Compiled by M. Rezaul Karim Tutul

where MSP, TSP, diammonium phosphate, ammonium sulfate, & other solid pH buffer ingredients are used, whether separately or in conjunction with another solid or liquid pH buffer ingredient, to influence dye bath pH. A high pH liquid buffer ingredient may be used to control pH of a scouring bath used to remove waste & oils from fibre or fabric. Desired pH for this operation is about 8-9.5. Following example illustrates this operation:

Example III
Into a suitable dyeing beaker containing an agitator, 25gm of 50% polyester, 50% cotton knit are placed in a bath of 500ml water. Then add surfactant & 0.15gm high pH liquid buffer ingredient No. 3. Bath is then heated to 180F & held for 10mins. Cloth scoured by this procedure using high pH liquid buffer ingredient No. 3 to control pH is of comparable cleanliness, brightness, & whiteness to cloth scoured in baths where solid phosphate pH control agents are used. A low pH liquid buffer ingredient may be used alone to set final pH of a bleaching bath about 6.08.0. Following example illustrates this operation:

Example IV
Into a suitable dyeing beaker containing an agitator, 10gm of cotton knit are placed in a bath of 200ml water. Next are added 0.2gm of a sequesting agent & 1.2gm of 35% hydrogen peroxide. Bath is heated to boil at 212 F & held for one hour. Bath is drained & cotton washed with 200ml water & 0.2gm low pH liquid buffer ingredient No. 2. Then cotton knit is washed again in 200ml of water. Neutralizations carried out in this manner with low pH liquid buffer ingredient No. 2 produce comparable results & fabric to neutralizations done with acetic acid, or other solid phosphate pH buffer agents. A low or high pH buffer ingredient may be used in different textile wet processing operations (bleaching, scouring, dyeing, printing or finishing) to neutralize the bath or the fabric. High pH buffer ingredient would be used to raise an existing low pH, & low pH buffer ingredient would be used to lower an existing high pH. One example of this type of use is to neutralize fabric & dye bath of a polyester/cotton blend after dyeing with disperse dyes & before dyeing with direct dyes. In addition to above applications of present invention, low &/or high pH liquid buffer ingredients find usage in a wide variety of industrial non-textile applications where processing in water systems occurs & setting &/or maintaining a desired pH is necessary. For example, solid buffer agents such as MSP or TSP are often used as ingredients in metal working lubricants which are water based. Low pH liquid buffer ingredients Nos. 1 or 2 &/or high pH liquid buffer ingredients Nos. 3 or 6 may be used as pH controls in these systems & produce comparable results when substituted for MSP or TSP. Solid buffer agents such as MSP or TSP are commonly used as pH control &/or buffers in wet processing of wood pulp in paper industry. Low pH liquid buffer ingredients Nos. 1 or 2 &/or high pH liquid buffer ingredients Nos. 3 or 6 may be used as pH control &/or buffer in pulp processing & produce comparable results when substituted for MSP or TSP. Although particular embodiments of present invention have been disclosed herein for purposes of explanation, further modifications or variations thereof will be apparent to those skilled in art to which this invention pertains.
Mechanism of Buffering System-Compiled by M. Rezaul Karim Tutul