Geotechnical and Geological Engineering (2006) 24: 11151130 DOI 10.

1007/s10706-005-1137-7

Springer 2006

Ferric chloride treatment to control alakli induced heave in weathered red earth
P.V. SIVAPULLAIAH
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and MANJU

Department of Civil Engineering, Indian Institute of Science, Bangalore, 560 012, India (Received 10 February 2005; accepted 12 July 2005) Abstract. A detailed experimental investigation has been carried out to study the use of ferric chloride salt to control the undesirable volume changes induced by high concentrated alkali contamination on kaolinitic red earth. X-Ray diraction studies have revealed that soil alkali interactions produce mineralogical changes and formation of new mineral such as zeolite, which are responsible for observed swelling in non-swelling kaolinitic soil. Loss of ferric oxide, which are known cementing agents has been attributed as one of the reasons for swelling in alkali contaminated soils. The consolidation behaviour of soil compacted with 5% ferric chloride solution by weight of solutions and inundated with alkali solutions as well as soil compacted with alkali and inundated with 5% ferric chloride by weight of solutions has been studied. To study the eect of amount of ferric chloride, the volume change behaviour of soil compacted with dierent weight percentages of ferric salts by weight of soil (1%, 3%, and 5%) and inundated with alkali solutions has also been studied. The swelling of soil compacted with alkali has been checked by inundating with 5% ferric chloride solutions due to neutralization of alkali and is not controlled when soil compacted with 5% ferric chloride solutions is inundated continuously with alkali solutions. Further, even when the soil is treated with higher amounts of ferric chloride, in the range of 15% by weight of soil, the swelling is not controlled. X-ray diraction studies have shown that the formation of zeolite is not inhibited in the presence of ferric salts.This study clearly shows that ferric chloride treatment can overcome the eects of small concentrations of alkali; it is ineective to overcome the large and continued exposure of soils with alkali contamination. Key words. alkali, consolidation, ferric chloride, kaolinite, swelling, zeolite.

1. Introduction
Weathering that occurs in sub-aerial environment is a complex interaction taking place between the aqueous solution and mineral solids.The most obvious indicator of weathering is oxidation with associated colour change. The interaction between water and minerals at the microscopic level consists of two basic processes: dissolution and re-precipitation (Righi and Meunier, 1995). The process of re-precipitation or re-crystallization can lead to the formation of clays, oxides and other secondary minerals from the aqueous solution. This usually introduces an important component of structure cementation. As a result, cementation usually bonds
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Corresponding author: P. V. Sivapullaiah, (Fax: +91-80-2360-0404, E-mail: siva@civil.iisc.ernet.in)

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particles together and can cause the formation of relatively large sti units aggregates. The Indian red soil consists of two species of Fe oxide. The amount of iron oxide minerals chemically (single extraction, using dithionite-citrate-bicarbonate reagents) extracted from the Bangalore red soil corresponds to 2% by weight (Rao et al., 1988). These compounds contribute to the aggregation of red soil particles. Studies have shown that weathered red soils, having kaolinite as main clay mineral, heave due to contamination with high concentrated caustic soda solution. Also in some cases it is known to cause reduction in the shear strength of soil (Sinha et al., 2003). The fundamental principles that has been considered generally to understand the behaviour of soil in the presence of contaminants of moderate or low concentration are in terms of (i) the type and amount of clay mineral (ii) the nature of pore uid, (iii) associated cations and anions (iv) organic matter. Relatively the eect of pore uid, cations and anions is very less for kaolinite minerals. Hence, the intense interactions that take place with some contaminants such as strong acid and alkali, which leads to disintegration of clay structure and changes in the mineralogy in the form of formation of new minerals/compounds, essentially control the behaviour of these soils. In this paper, an attempt has been made to understand the volume change behaviour of kaolinitic soils in the presence of alkali solution. A brief account of swelling in soils has been presented. Three main theories relating to swelling of cohesive soils are as follows:

1. Foster (1953, 1955) attempted to explain swelling in terms of clays as colloidal electrolytes. Swelling is associated with dissociation of cations leaving clay units with negative charges and thus repelling each other. 2. Baver et al. (1972) attempted to explain swelling by di-polar water hypothesis. It is said that replacing the adsorbed cations with cations of higher or lower hydration energies can alter the swelling characteristics of clay by Base Exchange method. 3. The third physico-chemical theory generally referred to as osmotic pressure hypothesis is based upon the analogy between the semi-permeable membrane of the classical osmosis experiment and the clay particle in water (Mitchell, 1976). For kaolinite clay minerals, whose specic surface area and cation exchange capacity are less, the eect of physio-chemical changes cannot be explained alone by these parameters. Causes for the heave/swelling of weathered red soil in the presence of alkali are mainly attributed to: 1. The dissolution of the iron oxide (cementing agent) coatings of the soil aggregates in the alkaline environment would act to release or disperse the soil particles held in aggregates which manifest as heave of the soil mass (Rao and Rao, 1994).

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2. Formation of new compounds on interaction of soil with highly concentrated alkali solution. As silica gets dissolve on treating the natural sample with 0.1 N sodium hydroxide (NaOH) solutions itself. The new mineral formed is of zeolite group, which is known for its swelling characteristics (Sivapullaiah and Manju, 2005). The relative inuence of the above two factors for swelling induced by alkali, however, is not known. The properties and occurrences of zeolites are summarized here. Zeolites are hydrated aluminosilicates with symmetrically stacked alumina and silica tetrahedral, which result in an open and stable three dimensional honeycomb structures with a negative charge. The negative charge within the pores is neutralized by positively charged ions (cations) such as sodium. Water moves freely in and out of these pores but the zeolite framework remains rigid. Another special aspect of this structure is that the pore and channel sizes are nearly uniform, allowing the crystal to act as a molecular sieve. The porous zeolite is host to water molecules and ions. Natural zeolites occur principally in unmetamorphosed sedimentary rocks and are particularly widespread in volcaniclastic strata. The pH is the most important chemical parameter in determining the rate of zeolitic reactions and at a pH of 9.5 substantial amounts of zeolites can form. Most zeolitic occurrences can be assigned to one of several types of geological environments or hydrological systems. These are (1) saline, alkaline lakes; (2) saline, alkaline soils and land surfaces; (3) sea-oor sediments; (4) percolating water in an open hydrologic system; (5) hydrothermal alteration; and (6) burial diagenesis. A wide variety of minerals react to form zeolite in the alkaline environment, reecting the solubility of Al and Si at high pH. Some common reactants are volcanic glass, biogenic silica, poorly crystalline clay, and quartz (Sand and Mumpton, 1976). Thus, zeolite minerals can form if source of alumina, silica and alkaline system is available. Mohnot et al., 1987 have reported a brief review of kaolinite-alkali reactions considering the possible eects. Al2 Si2 O5 OH4 2Na 2OH 2NaAlSi3 O8 11H2 O 4SiOH4 (Kaolinite) (Dissolved silica) (Na-Feldspar) 1 Al2 Si2 O5 OH4 5H2 O 2AlOH3 2SiOH4 (Kaolinite) (Gibbsite) (Dissolved silica) Al2 Si2 O5 (OH)4 2Si(OH)4 Al2 Si4 O10 (OH)2 5H2 O (Kaolinite) (Dissolved silica) (Pyrophillite) 2Si(OH)4 Al2 Si2 O5 (OH)4 2Na 2OH 2NaAlSi2 O6 H2 O 5H2 O (Zeolite) (Kaolinite) (Dissolved silica) 4 2 3

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2. Objective of the Study

The main objective of the study is to understand the inuences of presence of cementing agent in the alkali induced swelling in weathered red earth. Rao and Rao (1994) has suggested 5% ferric chloride solution as a stabilizing agent to reduce swelling in soil contaminated with 40% (10 N) caustic soda solution. If the removal of cementing compounds is the main reason, then treatment of alkali-contaminated soil with ferric chloride solution should restore the volume change behaviour. On the other hand if the swelling is predominantly due to formation of new minerals, then the eect of ferric chloride to prevent the formation of zeolite minerals could not be observed. X-ray diraction patterns have to be studied on the samples after consolidation tests carrying out on alkali contaminated soil with ferric chloride by dierent methods to conrm this mechanism. A detailed experimental program has been drawn to investigate the eect of ferric chloride on contaminated red earth soil with 4 N NaOH and industrial spent caustic liquor, which causes severe swelling.

3. Materials and Methods

3.1. SOIL USED The red soil used in the study was collected around the soil mechanics laboratory, Indian institute of Science, Bangalore, India. The soil was collected by open excavation, from a depth of 1 m from natural ground level. The soil was air dried and used after sieving through Indian Standard 425-l sieve. X-ray diraction of red earth has shown peaks at 7.2 A, 3.6 A and 1.49 A, which are diagnostic of the two-layered kaolinite mineral. The major minerals present, however, is quartz and showed strong peaks at 3.36 A and 4.28 A. It is not surprising that quartz is present as they are the most weathering-resistant primary minerals (Dixon and Weed, 1989), and tropical weathering has converted other primary minerals into clays oxides. The physical properties of the soil used are reported in Table 1. Silica, alumina, iron and other chemical constituents in the soils were analyzed according to standard methods (Hillerbrand and Lundel, 1953; Jackson, 1967). The results have been presented in Table 2 and are based on the oven-dried weight of the soil at 105 C. The base exchange capacity of the soils were determined as per Jackson (1958), along with the type of cations, and are reported in Table 2.

3.2. FLUIDS USED Chemically pure ferric chloride was obtained from Glaxo Laboratory, India. The uids used were (1) Distilled water, (2) industrial caustic Spent liquor solutions and (3) 4 N NaOH solution. Caustic Spent liquor was brought from Alumina extraction industry INDAL, India. Spent liquor is having a concentration of 4.5 N and is containing 20%

FERRIC CHLORIDE TREATMENT Table 1. Physical properties of red earth soil

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Property Specic Gravity Atterbergs Limits Liquid limit (%) Plastic limit (%) Plasticity index (%) Shrinkage limit (%) Free swell index (cc/gm) pH Specic surface area (m2/gm) Grain size distribution Clay content (%) Silt content (%) Fine sand content (%) Soil classication Standard Proctors Maximum dry unit weight (kN/m3) Optimum water content (%)

Red earth 2.67 38 19 19 15 1.2 7.67 75.55 22 44 34 CI 17.8 18.2

Table 2. Chemical composition and base exchange capacity of the red earth soil

Constituents Silica (SiO2) Alumina (Al2O3) Ferric (Fe2O3) Titanium (TiO2) Potassium (K2O) Sodium (Na2O) Magnesium (MgO) Calcium (CaO) Loss on ignition Base exchange capacity (meq/100 gms) Na K Ca Mg Total

Percentage 62.35 18.05 2.61 0.21 0.42 0.32 1.67 5.91 8.41 0.82 0.38 6.86 1.78 10.84

alumina by weight of solution. 4 N solution was prepared by dissolving the required amount of Analar Grade sodium hydroxide pellets in distilled water. 3.3. X-RAY DIFFRACTION STUDIES Randomly oriented samples were prepared by manual grinding in a porcelain mortar and pestle to powder form and subsequently pressing the material lightly into

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rectangular glass holders. X-ray diraction patterns were obtained using Philips X-ray diractometer model PW3710 and X1 advanced diraction system that has a provision to interchange X-ray tube. CuKa radiation was used for uncontaminated soil and for soil exposed to alkali solutions. However, to avoid high absorption of iron and background darkening due to uorescent radiation by CuKa from soil containing Fe, X-ray diraction patterns were obtained using Fea radiation for ferric chloride treated soil samples.

3.4. ONE-DIMENSIONAL CONSOLIDATION TESTS To analyze the eect of ferric chloride as stabilizer for controlling the heaving nature of high concentrated alkali contaminated red soil, one-dimensional consolidation test were conducted in conventional oedometer using dierent concentration of alkali and dierent percentages of ferric chloride. A load increment ratio of one was adopted and the load increment duration was kept as 24 h or until primary consolidation was complete. All the tests were conducted up to a pressure of 800 kPa. At a nominal pressure of 6.25 kPa, the sample was inundated with the required uid. In all the series, samples were loaded to 800 kPa, in the conventional manner and unloaded to 6.25 kPa in the same order as that was loaded.

4. Experimental Programme
Sample preparation and inundating uid in consolidation tests were varied to assess the eect of ferric chloride when incorporated in sample before contamination and when contaminated soil is treated. For conducting the tests for the former, the sample of red soil with water and ferric chloride is compacted to Proctors maximum dry density and optimum moisture content of uncontaminated soil and inundated with alkali solution. In the tests for the later, soil samples were compacted with alkali solution but inundated with ferric chloride solution. Before compacting, the specimens mixed with required quantity of alkali solution or ferric chloride were placed in polyethylene bags and stored in airtight container for about 34 days, for equilibration of moisture and then compacted. For comparison, consolidation tests were conducted on red soil compacted with water and inundated with water; compacted with water and inundated with alkali solution; compacted with alkali solution and inundated with water; and compacted with alkali solution and inundated with alkali solutions.

5. Results and Discussions

To assess the eciency of 5% ferric chloride solution in controlling the volume change behaviour of red soil, aected by 4 N solution and industrial spent caustic liquor, have been studied.

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5.1. EFFECT OF PASSING 5% FERRIC CHLORIDE SALT SOLUTIONS ON THE VOLUME

CHANGE BEHAVIOUR OF RED EARTH SOIL CONTAMINATED WITH 4 N CAUSTIC SODA SOLUTIONS

The void ratiopressure relationship for the soil remoulded with 4 N sodium hydroxide solutions and inundated with (i) the same solution, (ii) water, and (iii) 5% ferric chloride solutions are compared in Figure 1. The void ratiopressure relationship of uncontaminated soil is also shown for reference. It can be seen from the Figure 1 that the soil compacted and inundated with 4 N alkali solution undergoes relatively high compression and exhibits very steep rebound during unloading compared to that of uncontaminated soil. On remoulding with 4 N NaOH solutions, the dissolution of silica minerals from soil occurs, which reduces the strength of soil, and that leads to higher compression. The steep rebound during unloading has been attributed to mineralogical changes and formation of zeolite group of minerals, which are known to cause swelling in soils (Table 3 and Figure 2) (Kruglitskii et al., 1985; Kranz et al., 1989; Heidug, Wolfgang and Wong, Sau-Wai, 1996). By the time it reaches the end of loading cycle, more and more zeolite minerals would get formed, and causes swelling with decrease in the eective consolidation pressure during unloading. X-ray diraction study of consolidated specimen, compacted and inundated with 4 N NaOH solutions, has shown new peaks due to (NASH) 1.08Na2OAl2O31.68SiO21.8H2O Powder Diraction File Alphabetical indexes, Inorganic Phases (1990). When the contaminated soil is inundated with water, lower compression during loading and lesser rebound during unloading compared to sample compacted and inundated with 4 N NaOH solutions, is observed. The absent of abnormal

0.48 0.46 0.44 0.42 0.4 Red soil + 4 N NaOH 0.38 0.36 0.34 1 10 100 1000 + 4 N NaOH Red soil + 4 N NaOH + Water Red soil + 4 N NaOH + 5% FeCl3 Red soil + Water + Water

Void ratio

Pressure (kPa)
Figure 1. Eect of inundating 5% FeCl3 solution on soil compacted with 4 N NaOH solution.

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Table 3. Important mineralogical changes after ferric chloride treatment in alkali contaminated red earth

Compacting and inundating uids Water; 4 N NaOH 4 N NaOH ; 4 N NaOH 4 N NaOH, water Water; spent liquor Spent liquor; spent liquor Spent liquor; water 4 N NaOH; 5% FeCl3 Spent liquor; 5% FeCl3 5% FeCl3; 4 N NaOH 5% FeCl3+spent liquor 1% FeCl3*; 4 N NaOH 3% FeCl3*; 4 N NaOH 5% FeCl3*; 4 N NaOH 1% FeCl3*; spent liquor 3% FeCl3*; spent liquor 5% FeCl3*; spent liquor

d-Values of new compounds/minerals 3.60, 3.60, Nil 3.60, 3.60, Nil Nil Nil 3.64, 3.66, 3.64, 3.66, 3.66, 3.64, 3.66, 3.64, 6.45, 2.58 6.45, 2.58 6.45, 2.58 6.45, 2.58

Minerals Zeolite Zeolite Nil Zeolite Zeolite Nil Nil Nil Zeolite Zeolite Zeolite Zeolite Zeolite Zeolite Zeolite Zeolite (I) (I) (I) (I)

2.58, 2.55, 2.58, 2.55, 2.55, 2.58, 2.55, 2.58,

2.10 2.80 2.10 2.80 2.80 2.10 2.80 2.10

(II) (III) (II) (III) (III) (II) (III) (II)

Zeolite (I): sodium aluminium silicate hydrate (1.08Na2OAl2O31.68SiO21.8H2O) (PDF No. 31-1271). Zeolite (II): sodium aluminium silicate hydroxide hydrate (Na8(AlSiO4)6(OH)2 2H2O) (PDF No. 42-0215). Zeolite (III): sodium aluminium silicate hydrate (Na6(AlSiO4) 64H2O) (PDF No. 42-0216). *Salt by weight percentage of soil.

rebound has been attributed to, probably formation of lesser/no zeolite minerals due to reduced alkalinity of soil. On inundation with water, the alkalinity of soil reduced and thus formation of zeolite would not have taken place. It is supported from X-ray diraction patterns as tabulated in Table 3 and as shown Figure 2, by the absence of peak corresponding to (NASH) Zeolite (I) 1.08Na2OAl2O31.68SiO2 1.8H2O one form of zeolite. It has been observed that when the 4 N NaOH solutions contaminated soils is been inundated with 5% ferric chloride solutions, total compression during loading cycle and rebound during unloading is almost same as that of uncontaminated soil. No abnormal rebound during unloading is been observed and the behaviour of rebound is same as that of uncontaminated soil. The least compression might be due to (i) cementation of particles, which reduce the compression during loading or (ii) reduction in the concentration of alkali in the soil by passing ferric chloride solution, which is acidic in nature and would have prevented soil alkali reactions (Loughnan, 1969). X-ray diraction pattern (Table 3) has not shown the peak corresponding to Zeolite (I) 1.08Na2OAl2O31.68SiO21.8H2O one form of zeolite, signifying the predominance of rst mechanism. XRD studies carried out with CuKa radiation and under Fea radiation cannot be plotted in the same gure, as

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Figure 2. X-ray diraction pattern of consolidated kaolinite samples.

2h values will be dierent for two dierent X-ray sources. Thus mineralogical changes in ferric chloride treated samples are only tabulated in Table 3 in terms of d spacing.

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5.2. EFFECT OF PASSING 5% FERRIC CHLORIDE SALT SOLUTIONS ON THE VOLUME

CHANGE BEHAVIOUR OF RED EARTH SOIL CONTAMINATED WITH SPENT CAUSTIC LIQUOR

The void ratiopressure relationship for the soil remoulded with industrial caustic spent solution and inundated with (i) the same solution, (ii) water, and (iii) 5% ferric chloride solution is compared in Figure 3. It can be observed that the soil compacted and inundated with caustic spent liquor shows lesser compression during loading but exhibits steep rebound during unloading compared to untreated soil. XRD shows the formation of Zeolite minerals, and this is the reason for steep rebound during unloading (Table 3 and Figure 2). The dierence in the behaviour of soil treated with 4 N caustic solution and industrial spent caustic solution is due to the dierence in the composition of solutions and that is aecting the rate of formation of zeolite minerals. Spent liquor contains 20% of alumina by weight of solutions. For the formation of zeolite minerals, source of alumina and silica is needed. On increase in the source of reactant in any reaction, reaction shift to product, as every reaction tends to reach equilibrium. Thus on availability of external alumina, formation of zeolite would have formed faster with spent liquor and thus, less compression during loading cycle have been observed in specimen inundated with spent liquor. Swelling nature of Zeolite minerals would have resisted the compression. During loading cycle, soil compacted with caustic spent liquor and inundated with water shows higher compression than soil compacted and inundated with caustic spent liquor. However, during unloading cycle no abnormal rebound has been observed. The higher compression in specimen compacted with spent liquor and inundated with water is due to the dissolution of silica when remoulding with
0.5 0.48 0.46 0.44 0.42 0.4 0.38 0.36 0.34 1 10 100 1000 Red soil Red soil Red soil Red soil + Spent liquor + Spent liquor + Spent liquor + Water + Spent liquor + 5% FeCl3 + Water + Water

Void ratio

Pressure (kPa)

Figure 3. Eect of inundating 5% FeCl3 solution on soil compacted with spent liquor solution.

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spent liquor. And no abnormal rebound during unloading is due to no formation of zeolite minerals due to less alkaline nature of soil, as soil is inundated further with water. No zeolite peak is seen in the XRD of this consolidated soil sample (Table 3 and Figure 2). From Figure 3 it can be seen that soil compacted with caustic spent liquor and inundated with 5% ferric chloride solutions, compression and rebound is less than the soil compacted with caustic spent liquor and inundated with water. This could be more due to eective neutralization of alkalinity of soil by ferric chloride solution than by water. From the above discussion, it appears that passing ferric chloride solution to the alkali-contaminated soil inhibits soil-alkali reactions. Under this condition high amount of ferric chloride solution is available and soil is not contaminated with further alkali contamination. And this may be the reason for observing no swell during the consolidation test. Another set of experiments have been conducted wherein the soil is treated with 5% ferric chloride and inundated with alkali solutions during consolidation testing to asses its suitability as stabilizing agent. The results of these studies are presented in the following paragraphs. 5.3. VOLUME CHANGE BEHAVIOUR OF SOIL TREATED WITH 5% FERRIC CHLORIDE
SALT SOLUTION DURING CONTAMINATION WITH 4 N NAOH SOLUTION

Figure 4 shows the void ratiopressure relationship for soil compacted with 5% ferric chloride solution to Proctors maximum dry density and optimum water content of uncontaminated soil and inundated with 4 N caustic soda solution. The void ratiopressure relationship of uncontaminated soil and soil compacted with

0.72 0.67 0.62

Void ratio

0.57 0.52 0.47 0.42 0.37 0.32 1 10 100 1000

Red soil + 5%FeCl3 + 4 N NaOH Red soil + Water + Water Red soil + Water + 4 N NaOH

Pressure (kPa)

Figure 4 Eect of inundating 4 N NaOH solution on soil compacted with 5% FeCl3 solution.

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water and inundated with 4 N NaOH solutions are also given for reference. It can be seen from Figure 4 that soil compacted with water and inundated with 4 N caustic soda solution shows abnormal swelling during unloading compared to that of uncontaminated soil. The compression strain has completely been recovered upon unloading. Final void ratio of the specimen is signicantly higher than the initial void ratio of the sample. This conrms the formation of swelling compounds. From XRD studies of this soil sample, it has been established that Zeolite (I), new minerals are formed due to soil alkali interaction (Table 3 and Figure 2). The soil compacted with 5% ferric chloride salt solution and inundated with 4 N NaOH solutions continues to show abnormal rebound during unloading as that of soil compacted with water and inundated with 4 N NaOH solutions. It can be seen from XRD (Table 3) that soil treated with 5% ferric chloride salt solutions and inundated with 4 N alkali solution also shows the presence of zeolite minerals (Na8(AlSiO4)6(OH)2 2H2O, Zeolite (II)), indicating that ferric chloride solution cannot prevent the formation of swelling compounds which cause abnormal volume change behaviour. 5.4. VOLUME CHANGE BEHAVIOUR OF SOIL TREATED WITH 5% FERRIC CHLORIDE
SALT SOLUTION DURING CONTAMINATION WITH SPENT LIQUOR

Figure 5 shows the void ratiopressure relationship for soil compacted with 5% ferric chloride solution and inundated with caustic spent liquor solution. Here also the void ratiopressure relationship of uncontaminated soil and soil compacted with water and inundated with caustic spent liquor solutions are given in Figure 5. It can be seen from Figure 5 that soil compacted with water and inundated with caustic spent liquor solution shows abnormal swelling during unloading compared to that of

0.56 0.54 0.52 0.5

Void ratio

0.48 0.46 0.44 0.42 0.4 0.38 1 10 100 1000

Red soil + 5% FeCl3 + Spent liquor Red soil + Water +Water Red soil + Water + Spent liquor

Pressure (kPa)

Figure 5. Eect of inundating spent liquor sol. on soil compacted with 5% FeCl3 solution.

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uncontaminated soil. Here also compression strain has been completely recovered upon unloading. From XRD studies of this consolidated soil sample, it appears that Zeolite (I) (1.08Na2OAl2O31.68SiO21.8H2O) has formed due to soilalkali interaction (Table 3 and Figure 2). The soil compacted with 5% ferric chloride salt solution and inundated with caustic spent liquor solutions also shows abnormal rebound during unloading as that of soil compacted with water and inundated with caustic spent liquor solutions. From XRD (Table 3) it can be seen that 5% ferric chloride salt solutions treated soils shows the presence of zeolite minerals, Zeolite (III) (Na6(AlSiO4)64H2O) (Na8(AlSiO4)6(OH)22H2O), in the continued contamination with spent liquor solution. It shows that treatment with ferric chloride is unable to prevent the adverse eect of alkali contamination.

5.5. USE OF HIGHER AMOUNT OF FERRIC CHLORIDE SALT TO COUNTER THE EFFECT
OF ALKALI SOLUTIONS ON VOLUME CHANGE BEHAVIOUR OF SOIL

From the above results it appears that the soil treated with 5% ferric chloride salt solution by weight of solution is not enough to stop heaving of red soil due to alkali contamination and prevent the formation of new mineral such as zeolite. This might be due to limited amount of ferric chloride that has been incorporated in the soil while getting contaminated with large alkali concentrations. To overcome this limitation, the soil has been treated with dierent percentages of ferric chloride salt and consolidation tests were conducted with alkali solutions as inundating uid. The amount of ferric chloride salt has been varied from 1% to 5% by weight of soil.

5.6. VOLUME CHANGE BEHAVIOUR OF SOIL TREATED WITH DIFFERENT AMOUNTS

OF FERRIC CHLORIDE SALT AND INUNDATED WITH 4 N NAOH

Figure 6 shows the void ratiopressure relationships for the red soil mixed with 1%, 3%, and 5% ferric chloride salt by weight of soil and compacted to Proctors maximum dry density and optimum water content of uncontaminated red soil and inundated with 4 N NaOH solution. When the soil is been mixed with 1% ferric chloride salt by weight of soil and inundated with 4 N NaOH solutions, the volume change behaviour during loading as well unloading is more or less same as that of soil compacted without salt and inundated with 4 N NaOH solutions (Figure 6). This shows that the eect of 1% ferric chloride salt is negligible. XRD of sample treated with ferric chloride also shows the peaks of Zeolite mineral, Zeolite (II) (Table 3). Earlier it has been noticed that when the soil is contaminated with small amount of 4 N alkali solution and inundated with ferric chloride solution, alkali eect is not seen due to neutralization of alkali concentration. However, in this case, soil alkali reactions proceed and 1% ferric chloride is unable to prevent formation of Zeolite minerals.

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0.6

Void ratio

0.5

0.4 Red soil + 1% FeCl3+ 4 N NaOH Red soil + 3% FeCl3 + 4N NaOH Red soil + 5 % FeCl3 + 4N NaOH 0.2 Red soil + Water + Water Red soil + Water + 4N NaOH 0.1 1 10 100 1000

0.3

Pressure (kPa)
Figure 6. Eect of inundating 4 N NaOH solution on soil compacted with dierent percentage of FeCl3 salts.

When the soil is mixed with higher amounts of ferric chloride salt and inundated with 4 N NaOH solutions, compression is almost same as that of soil mixed with 1% ferric chloride salt, and inundated with 4 N NaOH solutions. Rebound curves of specimen treated with various percentages of FeCl3 are parallel up 50 kPa, but after this pressure range, amount of change in the void ratio is in the order of 1%>3%>5% ferric chloride treated samples. In XRD study of these consolidated soil samples peaks corresponding to zeolite mineral have been observed (Table 3). The small dierences in the amount of rebound due to presence of various percentages of ferric chloride salts are due to amount of eective neutralization of alkalinity of soil because of acidic nature of ferric chloride. However, the reduction of alkalinity of the soil due to presence of FeCl3 salt was not sucient, even with 5% FeCl3 by weight of soil, to hinder the formation of zeolite minerals, as XRD studies have shown the formation of dierent composition of Zeolite minerals. Thus addition of ferric chloride is unable to cease the alkali induced heave in weathered red soil. 5.7. VOLUME CHANGE BEHAVIOUR OF SOIL TREATED WITH DIFFERENT AMOUNTS OF
FERRIC CHLORIDE SALT AND INUNDATED WITH INDUSTRIAL CAUSTIC SPENT LIQUOR SOLUTION

Figure 7 shows the void ratiopressure relationships for the red soil mixed with 1%, 3%, and 5% ferric chloride salt by weight of soil and compacted to Proctors maximum dry density and optimum water content of uncontaminated red soil and inundated with industrial spent liquor. Soil mixed with 1% ferric chloride and

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0.53

0.48

Void ratio

0.43

0.38 Red soil + 1%FeCl3 + Spent liquor Red soil + 3% FeCl3 + Spent liquor 0.33 Red soil + 5% FeCl3 + Spent liquor Red soil + Water + Water Red soil + Water + Spent liquor 0.28 1 10 100 1000

Pressure (kPa)

Figure 7. Eect of inundating spent liquor solution on soil compacted with dierent percentage of FeCl3 salts.

contaminated with spent liquor shows higher compression and steep rebound during unloading as that of soil without salt. This shows that 1% salt has not improved the volume change behaviour of soil contaminated with liquor. Even on increased salt content, very marginally dierence in the amount of rebound occurred. X-ray data has again conrmed the formation of zeolite minerals with any amount of ferric chloride in the presence of spent liquor solution (Table 3). Thus, formation of zeolite would have continued even in the presence of ferric chloride salt. As on addition of NaOH solutions to the soil treated with ferric chloride salt, reaction between NaOH solution and ferric chloride will lead to the formation of ferric hydroxide as a precipitate, which is inert in nature. Thus its presence would not have inhibited the formation of Zeolite minerals unless the soil system is alkaline in nature.

6. Conclusions
1. Higher compressions and rebound caused by alkali solutions (due to formation of Zeolite Minerals) are better controlled by passing 5% ferric chloride solution than passing water through dilution of the alkali concentration. 2. When the soil is exposed continuously to alkali solution and soil treatment with 5% FeCl3 solution by weight of solution, reduces the amount of rebound during oedometer test marginally and the formation of swelling compounds is not inhibited. 3. Even addition of FeCl3 by weight of soil could not control the alkali induced swell in kaolinitic soils as formation of zeolite continues as soil system remain highly alkaline in nature.

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P.V. SIVAPULLAIAH AND MANJU

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