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TANNING TECHNICAL CHEMISTRY I: PRACTICALS

 

IGUALADA TANNING SCHOOL

 

 

 

Igualada Technical Engineering School




          Technical University of Catalonia (UPC)

 

 

 



PRACTICAL NUMBER 1:
SIMULATION OF BUFFER IN DELIMING.

AIMS:    
        
1. The aim is to simulate the neutralization of the alkalinity of the hide after liming by using a dissolution of sodium hydroxide.
2. The aim is to observe the possible formation of buffer solutions and if so, the pH values that are obtained.
3. This can also be useful when comparing the deliming power inherent to different products.
         
MATERIAL :

Beakers; glass rod; a 50mL burette; pH-indicator paper (i.e. litmus paper). If possible use a pH-meter.
       
PRODUCTS :

Sodium hydroxide; ammonium sulphate; acetic acid; lactic acid; chloridric acid; sodium bisulphite; commercial deliming (both solid and liquid); formic acid, hydrochloric acid.
           
PROCEDURES:

- Prepare a 250 mL solution with 3% of sodium hydroxide and 100 mL solutions with 10% of each of the remaining products.
- Take 25 mL of the solution of sodium hydroxide and measure its pH and slowly add a solution of ammonium sulfate (adding 5 mL at a time). Shake briefly after each addition, observe and measure the pH. Repeat this operation until 100 mL of ammonium sulfate have been added or until the pH values remain constant with the new additions.
-Repeat the same operation with the remaining commercial deliming products.
- Graph the results by putting the pH values on the y axis and the added mL of the acid-deliming products on the x axis.

DISCUSSION AND CONCLUSIONS :

- Observe whether a buffer is formed and if so, the pH values at which it is formed.
-Draw a comparison between the values obtained when using different deliming products both in relation to the formation (or non-formation) of buffer solutions and to the amount that is needed in order to neutralize the same amount of sodium hydroxide (25 mL in this experiment).
-Draw conclusions.
























                                              PRACTICAL NUMBER 2:

                                                 CHROME SALTS
                                              

AIM:

1. The aim is to observe the effects of masking and basicity on chrome salts and, provided that it is possible, to observe the effects on the hide treated with chrome salts of different basicities and degrees of masking.
2. The proportions of products used in this practical will sometimes be increased a lot so that the effects can be observed more clearly. 

MATERIAL:
Beakers; glass rod; pH-indicator paper (i.e. litmus paper) or pH-meter; a 10 mL graded pipette or a 50 mL burette, thermometer.

PRODUCTS:

Chrome salt with 33% basicity and another salt with higher basicity; sodium carbonate; formic acid; sodium bicarbonate; etilen-diamine-tetra-acetate-disodium = (Edtna) or any type of industrial masking; hydrogen peroxide; oxalic acid; sucrose or glucose; sodium or potassium dichromate; sodium formate.


1- PREPARATION OF A CHROME LIQUOR: 


Note: This experiment must be carried out carefully. Only use the right amounts, never use more than the given amounts. The amounts of both dichromate and sulphuric acid should only be the ones given. On the other hand, the amount of sucrose can be modified.

PROCEDURES:

- Weigh 20 g of either potassium or sodium dichromate in a precipitate vessel of 500 mL or bigger, partially dissolve them in 40 mL of water.
- Prepare 25 mL of a dissolution of sucrose or glucose at 30%.
- Add 20 g of sulphuric acid slowly and shake in order to complete the dissolution of dichromate (the heat that is released when the sulphuric acid dissolves favours both the dissolution of the dichromate and the beginning of the reaction with the reducing agent).
- Before it cools down, add 20 mL of the dissolution of sucrose or glucose very slowly and carefully. If it all works out accordingly, there will be a release of gases and vapor which are either a little toxic or uncomfortable and the high temperature is maintained or is even increased (i.e. exothermic reaction).
- Once the addition is finished, leave it to one side until the following day.
- Check the colour of the resulting liquor. The presence of a yellow shade indicates that the dichromate has not been fully reduced to chrome sulfate. In order to detect this, an analysis can be carried out determining the residual oxidation power compared to the potassium iodide (IK) with a starch indicator, among others.
- If chrome is detected in the form of dichromate, the reduction can be fully completed by adding some more mL of a solution of sucrose or glucose and carefully heating up the dissolution to boiling point.
- If we wanted to obtain a liquor with 43% basicity instead of a chrome liquor with 33%, then we should only use 18 g of sulphur acid instead of 20 g.
- If we wanted a liquor with 53%, then we should use only 16 g of sulphuric acid instead of the 20 g suggested in this experiment.
- Note: Generally, in reductions at an industrial level, the dissolution does not need to be heated up since the heat of the reaction is enough to fully complete the reduction of the dichromate.



2- MASKING OF CHROME SALT IN POWDER:

PROCEDURES :

- Prepare about 100 mL of a chrome salt dissolution with 33% basicity at a concentration of 10%.
- After dissolving it in cold water, measure its pH, keep half of the dissolution and leave it until the following day.
- Heat up the other half of the dissolution to boiling point, let it cool briefly and measure its pH.
- Repeat the process with another type of chrome salt with different basicity (42%) but always using chrome salt in powder form.
- According to the pH values obtained from the results, try to draw conclusions concerning the labile masking caused by the sulphates.

3- CHROME MASKING:


PROCEDURES :

- Prepare about 100 mL of a chrome salt dissolution with 33% basicity at a concentration of 5%.
- At the same time prepare about 20 mL of masking dissolutions at concentrations of 1%, 3% and 5%. Measure the pH of these dissolutions and adjust them to the approximate value of 3,5 by adding formic acid.
- Mix 2.5 mL of the chrome solution with 7.5 mL of the masking solution at 1%. Then shake it and observe any changes in colour and /or precipitations and measure its pH.
- Divide the dissolution in two and leave half of it to one side until the following day.
- Heat up the other half of the dissolution until it boils and maintain for five minutes. After that, leave it to cool down slightly and watch out for any changes of colour or possible precipitations, and finally measure its pH.
- Repeat the whole process mixing 5.0 mL of the chrome salt solution with 5.0 mL of the Masking solution at 1%.
- Repeat the whole process mixing 7.5 mL of the chrome salt solution with 2.5 mL of the Masking solution at 1%.
-In order to further study this phenomenon, the procedures of the process will be repeated using the the highest concentrations of the masking solutions.
- Compare the results in changes of colour, pH values, possible precipitations among the solutions that were analysed immediately, the ones that were left to one side, the ones that were boiled and try to draw conclusions.
- Repeat the whole process using oxalic acid instead of Edtna-2 as masking.
- Compare the two types of masking and draw conclusions.


4-DETANNING SIMULATION:


PROCEDURES:

- Prepare a 100 mL solution with 8% of chrome salt of 33% basicity by heating it up and leaving it to cool.
- Likewise, prepare a 50 mL solution with 8% of sodium carbonate, as well as a 25 mL dissolution with 8% of oxalic acid.
- Add about 25 mL of a  chrome salt solution and  25 mL of a sodium carbonate solution (slowly and shaking). After the addition and when the CO2 is fully released, measure the pH and observe precipitates.
- Slowly heat up to boiling point, leave it to cool, then measure the pH and observe precipitates if there are any.
- Repeat the same steps with the sodium carbonate but instead of heating it up, very slowly add 25mL of hydrogen peroxide (DO NOT HEAT). Observe any changes in colour and any other phenomena.
- To the 25mL solution of chrome salt, add a 25mL solution of oxalic acid, shake and observe possible colour changes.
- Slowly heat up to boiling point, observe again, measure its pH and leave it to rest. After one day, check for any new changes.
- The experiment with the sodium carbonate can be replicated using other alkali products such as sodium bicarbonate, ammonium hydroxide, etc. (Always add the alkali product to the chrome salt solution slowly and carefully).









PROCEDURES TO FOLLOW CONCERNING THE WRITING AND PRESENTATION OF THE REPORTS ON THE PRACTICALS


All the reports on the practicals should follow these criteria:

1. Aim: A brief description of what the student studies and attempts to do in each of the practicals in this module. (5%)

2. Theoretical basis: Research information related to the topics of study for each of the practicals, both in the textbook and from other sources. (35%)

3. Material and products:  List all the materials and products that have been used in all of the practicals.(Note the purity of each of the products used). (5%)

4. Methodology: Provide a description of how the practicals have been carried out. This implies the material and products that have been used, the working procedures, etc. (15%)

5. Calculations, results and assessments: This refers to the results that the student has come up with during the practicals. (15%)

6.Conclusions: Observations regarding the final result. (10%)

7. Bibliography: Write a bibliography for all the references that have been consulted while writing the report. (!5%)










AGENT, DELIMING: Acidic salt or acid salt or acid used to neutralise the lime and/or other alkali in limed pelt and so lower its pH

CAPACITY BUFFER: The ability of a solution, e.g. of a vegetable tannin infusion, to resist charge of pH on addition of acid or alkali

BRIDGE, OL: An OH group joining two metallic ions in a playnuclear complex –Cr-OH...Cr–

BRIDGE, OXO: An Oxigen atom joining two metallic ions in a polynuclear complex –Cr-O-Cr–

AGEING: The growing-old of a chrome tanning liquor,during which it un dergoes changes in chemical constitution, e.g. hydrolysis, migration of ions, olation, etc., or of mineral-tanned leather during wich the tanning agent becomes more firmly fixed

BOND, CHELATE: A more or less firm two-point attachment to or ion, with two or more active groups, e.g. ethylene diamine, oxalic acid, ethylene tetramine, acetic acid, thus forming a ring

AGENT, MASKING: Acids or their salts, whose anions enter the chromium complex, thereby hindering the penetration by the complex-active collagen groups and producing a milder tanning action and a more uniform chromium distribution throughout the leather thickness

BASICITY: The relationship between the chromium present in a trivalent chrome agent liquor, or a chrome-tanned leather, and the acid radicals associated with it. Measured in various ways

BASICITY, SCHORLEMMER (percentage): A method of expressing the basicity of a trivalent chrome tanning salt in terms of the percentage of the possible number of hydroxyl groups with which the chromium could combine, of those with which it is actually combined; passes from 0 in a normal salt to 100 in chromium trihydroxide

BASIFICATION: The processo f rendering a chrome liquor more basic, either before use or during tannage, by addition of a solution of an alkaline substance, e.g. sodium bicarbonate or carbonate




                                                                                                    

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