Class Objectives

Define D fi C Conductance d Define hardness Types of Hardness Problems caused by Hardness Identification of hard water Removal Methods Analytical Methods Bar Diagram Lab Procedure

Conductance
Ability of water to conduct electric current Water contains charged ions; all ions conduct electricity (Does DDI water conduct electricity?) Inverse of resistance Units mS/cm (millisiemens/cm) Measurement of gross chemical characteristics h t i ti Conductance affected by ion concentration and temperature
Increase in ion conc. increase in conductance Increase in temp. increase in conductance

Used to estimate Total Dissolved Solids

TDS (mg/L)=k*C (mS/cm) K varies i f from 0 0.5-0.9 509d depending di on i ion concentration and temperature (usually k=0.64) Monitoring salt content in irrigation water, industrial water, and desalination plants

Hardness
Hard H d water t Water with high mineral content Refers to the ability of the water to precipitate soap (phrase coined as the water does not lather well, soap consuming capacity) Sum of all polyvalent cations (Xi+n) Mostly Ca+2 and Mg+2 Also Sr+2,Fe+3,Fe+2,Mn+2,Al+3. Associated anions HCO3-, CO3-2, SO4-2, NO3-, and Cl-

Degree of hardness Soft Moderately Soft Slightly Hard Moderately Hard Hard V.Hard

Hardness, mg/L CaCO3 <50 50-100 100-150 150-200 200-300 200 300 >300

Types
Carbonate Hardness Also Temporary Hardness CO2 from atmosphere or CO3 from limestone or other rocks dissolve in water. Exists predominantly as HCO3- at natural pH ranges and df forms soluble l bl C Ca(HCO (HCO3)2 & Mg(HCO M (HCO3)2 salts. Can be removed by boiling or adding slaked lime (Ca(OH)2) Ca(HCO3)2 CaCO3+CO2+H2O Ca(HCO3)2 + Ca(OH)22CaCO3+ 2H2O Non carbonate hardness Also permanent hardness Caused mainly by CaSO4, MgSO4, CaCl2, MgCl2 Sources: Limestone, gypsum and other rock formations Cannot C tb be removed db by b boiling, ili i in f fact t more soluble l bl in higher temperatures heat Total Hardness Sum of temporary and permanent hardness Usually Ca+2 + Mg+2

Problems Caused by Hardness

Domestic
Requires large amount of soaps for washing and cleaning Causes soap p scums in showers, , bathtub, , and dishes (insoluble Ca and Mg salts of fatty acids in soaps) Leaves skin and hair rough Coats the inside of teapots and other utensils increasing the energy cost of heating. Also ruins the water heater and dishwashers.

Industrial
Clogs pipes Forms scaling in boilers, cooling towers, and other industrial equipments Decreases efficiency y and increases power p cost. Needs constant monitoring to avoid costly breakdowns.

Identifying Hard Water

Best way to determine if the water is hard or not is to experimentally test it. However, we can usually detect hard water by the evidence in your home.
Increased water heating costs (due to scale buildup & mineral deposits) Soap scum on bathtubs, shower tiles, shower heads etc Film left on body resulting in dry skin, dull/limp hair Reduced cleansing ability of soap Dull clothes dingy yellow laundry Buildup of scales on plumbing fiscures, tea kettles, pasta pot Clogged pipes resulting in decreases flow and increased repairs

Removal Methods
Temporary T Hardness H d
Boiling and filtering
The precipitation of CaCO3 is reversible. Boiling removes CO2 from water and reduces HCO3- concentration When cooled down CO2 redissolves and forms bi-carbonate

Adding Slaked lime and filtering

pH HCO3-, CO3-2

Most domestic and industrial problems caused by temporary hardness.

Removal Methods
Permanent P Hardness H d
Water Softening
Cation Exchange Add soda ash(Na2CO3) Ca+2 + Na2CO3 CaCO3 +2Na+ Filtering after softening removes CaCO3

Ion Exchange resins

Exchanges Ca+2, Mg+2 for Na+ Resins can be recharged by passing NaCl brine brine.

Advantages
2 and CO3-2 d HCO3- are natural l buffers required to maintain habitable pH in water Reduces corrosion and introduction of toxic metal species in water g+2 mitigates g the Ca+2 and Mg effects of high Na+ in soils and blood.

Test for Hardness

Ion Chromatography
Quantitative analysis for common anions and cations Accurate method Uneconomical/ inaccessible

Atomic Absorption Spectrophotometry

Analytical technique used to measure a wide range of cations Accurate method Uneconomical/ inaccessible

EDTA Titration Method

Stochiometric determination EDTA Titration using EBT indicator Economical method

Bar Diagram
G Graphical hi l method th d t to estimate ti t diff different t types of hardness and to perform cation anion balance. Used U d to estimate i the h li lime requirements i i in softening process. All species concentrations must be expressed either as meq/L or mg CaCO3/L CO2 is always the first component in the graph and is common to cations and anions Order of cations : Ca+2, Sr+2, Mg+2, other polyvalent cations, other monovalent cations. Order of anions: OH-, CO3-2, HCO3-, SO4-2, polyvalent y anions, , other monovalent other p anions

Bar Diagram g

Construct a bar diagram using following data obtained from a water sample. The carbon dioxide concentration was measured to be 2 mg/L.

Ion Ca+2 Mg g+2 Na+ K+ HCO3SO4-2 ClBr-

Conc ppm 100 15 25 8 330 49 37 10

Perform Cation anion balance a.) Total alkalinity (mg/L as CaCO3) b) Total hardness (mg/L as CaCO3) c) Carbonate hardness (mg/L as CaCO3) d) Non-carbonate hardness (mg/L as CaCO3) e) Calcium carbonate hardness (mg/L as CaCO3) f) Calcium C l i non-carbonate b t h hardness d (mg/L as CaCO3) g) Magnesium carbonate hardness (mg/L as CaCO3) h) Magnesium non-carbonate hardness (mg/L as CaCO3)

Bar Diagram
Ion Ca+2 Mg+2 Na+ K+ CO3HCO SO4-2 ClBrCO2
Eq wt. wt Conc C M Wt ppm g/mole 100 40 15 24 25 23 8 39 330 61 49 96 37 35.5 10 80 2 44 meq/L mg CaCO3/L

Hardness Procedure
1. M 1 Measure 25 25mL Lt tap water. t 2. Dilute the sample using 25mL distilled water. 3. Add 1-2mL buffer solution to raise pH to 1010 1 10.1. 4. Check pH. If pH=10, proceed to step 5. 5. Add 1-2 drops of EBT until you see the color change to wine red. 6. Add EDTA slowly with continuous stirring until the reddish tinge disappears. 7. Add the last few drops at 3-5 second intervals until the solution turns blue blue. 8. Use H = (1000 * Vt * M) / Vs Where H = hardness in mg/L as CaCO3 Vt = volume of EDTA added M = mg CaCO3 equivalent of 1 mL of EDTA = 1 Vs = volume of sample

Principle:
EDTA (ethylenediaminetetraacetic ( th l di i t t ti acid) id)
Is clear liquid. Forms stable complexes with metals. It first reacts with Ca2+ and then with Mg2+.

Erichrome Black T (EBT)

Is blue in color. Only reacts with Mg2+ (forming a metal complex with Mg). EBT turns wine red when it reacts with Mg g2+. Magnesium ion must be present to yield a satisfactory end point. EBT is added to mark the endpoint of the titration.

The p pH must be ~ 10 for the reaction to occur Titration must be done within 5 minutes of adding buffer EBT (Blue)+Mg+2 EBT Mg Complex (wine red) EDTA + Ca+2 EDTA Ca complex 2 EDTA Mg complex EDTA + Mg+2 EDTA + EBT Mg Complex EDTA Mg Complex + EBT (blue) p The endpoint p The blue color indicates the endpoint. indicates that the amount of EDTA consumed is equal to the amount of hardness metals present.