Direct Current Magnetic Field and Electromagnetic Field

Effects on the pH and Oxidation-Reduction Potential

Equilibration Rates of Water. 1. Purified Water
Masumi Yamashi ta,*
,
Chri s Duffi el d,

and Wi l l i am A. Ti l l er

Department of Geophysics and Department of Materials Scienceand Engineering,

Stanford University, Stanford, California 94305
Received March 24, 2003. I n Final Form: April 25, 2003
Effects of l ow l evel magneti c and el ectromagneti c fi el ds (bel ow B 100 mG for ac magneti c fi el d, and
bel ow B 1000 G for stati c magneti c fi el d), on puri fi ed water that i s i n the process of equi l i brati on, were
i nvesti gated. The pH and oxi dati on-reducti on potenti al (ORP)of di sti l l ed and dei oni zed water, previ ousl y
stored for ai r equi l i brati on, were measured after exposure tomagneti cfi el ds (acand dc)of di fferent strengths.
Readi ngs showed sl ow and l arge fl uctuati ons (0.05-0.1 pH uni t, 60 mV for ORP) duri ng the fi rst
several hours. These readi ngs l ooked decepti vel y stabl e due to the extreme sl owness of the fl uctuati ons.
When readi ngs were taken beyond thi s peri od, for days, the pH and ORP general l y changed sl owl y toward
equi l i bri um val ues i n a quasi -l i near fashi on. They changed faster, on average, i n those sampl es that had
been exposed tohi gher magneti c fi el ds. Readi ngs i n water sampl es often got stuck, remai ni ng unchanged
over an extended peri od before starti ng tochange agai n, when stored for equi l i brati on wi th ai r and measured
i n a mu-metal shi el d, where the ac magneti c fl ux was 0 mG (zero fi el d). These resul ts i ndi cate that, to
accuratel y eval uate the effects of weak magneti c fi el ds on water, subtl e experi mental condi ti ons such as
di fferenti al fi el d condi ti ons produced by common l ab devi ces and procedures, and background l ab fi el ds,
cannot be i gnored. Moreover, extendi ng measurements beyond several hours may be essenti al to rel i abl y
observe the presence or absence of these effects.
Introduction
I t i s wel l -known that water exhi bi ts a wi de range of
anomal ous behavi ors wi th respect to i ts vari ous materi al
properti es.
1-4
The l i terature on the subject i s vast and
often confusi ng, coveri ng a vari ety of spati al si ze scal es
as wel l as temporal response ti mes. The spati al si ze scal es
can be conveni entl y di vi ded i nto three categori es: (1)
mol ecul ar l evel properti es, i ncl udi ng water cl usters, wi th
the system consi dered tobe effecti ve si ngl e phase water
and homogeneous on a si ze scal e of 10
-7
to 10
-6
cm, (2)
two-phase or pol yphase water properti es associ ated wi th
ei ther cl assi cal cri ti cal poi nt phenomena or cooperati ve
i nternal el ectromagneti c (EM) mode i nteracti on phenom-
ena, wi th thi s si ze scal e bei ng treated as an effecti ve
si ngl e phase and homogeneous on a si ze scal e of <10
-5
to
10
-4
cm, and (3) a heterogeneous system of the foregoi ng,
pl us forei gn bodi es such as H
2n
O
n
water cl usters, col l oi ds,
l ong chai n mol ecul es, mi croscopi c gas bubbl es, space
charge l ayers, and so forth.
Temporal si ze scal e changes for phenomena i n categori es
1 and 2 run from pi coseconds toseconds, whi l e for category
3 they can run from seconds to days. The confusi ng
pl ethora of experi mental data on water i s somewhat
confi rmed by the remarkabl e fact that more than twodozen
water potenti al energy functi ons are i n regul ar use today
for vari ous computer si mul ati on acti vi ti es.
5
The i mportance of category 3 above i s that, i n an aqueous
el ectrol yte, these mi croscopi c moi eti es i nteract i n uni que
ways wi th the ambi ent el ectri c, magneti c, and EM fi el ds
so as to move them i n certai n di recti ons i n thei r macro-
scopi cenvi ronment. I n turn, thi s produces: (a)macroscopi c
spati al concentrati on changes i n these moi eti es, l eadi ng
to macroscopi c property vari ati ons i n overal l sol uti on, (b)
acti vati on of l ocal thermodynami c forces to recreate, at
some ki neti cal l y l i mi ted rate, the equi l i bri um popul ati on
of such moi eti es i n the regi ons dynami cal l y vacated, and
(c) acti vati on of such forces to aggl omerate or coagul ate
such moi eti es i n the overl y enri ched regi ons of the
macroscopi c sol uti on (at rates determi ned by the uni que
ki neti cs of these processes). Most of thi s i s strai ghtforward
physi cal chemi stry of many i nteracti ng processes whi ch
have not been recogni zed by many experi menters.
I n addi ti on to the foregoi ng, three envi ronmental
i nfl uences that have not been careful l y control l ed by
vari ous experi menters duri ng thei r studi es are (1) dc
magneti c fi el d and EM fi el d i ntensi ti es and gradi ents, (2)
convecti on mode and i ntensi ty, and (3)l i ghti ng mode and
i ntensi ty. Al l three of these envi ronmental i nfl uences
appear toi mpact the experi mental resul ts of vari ous water
studi es, and are i n need of careful i nvesti gati on.
6-12
I n
thi s seri es of papers, we l argel y focus on i tem 1 and a l i ttl e
* Towhom correspondence shoul d be addressed. E-mai l : masmi @
pangea.stanford.edu. Tel ephone: (650) 322-4739.

Department of Geophysi cs.

Department of Materi al s Sci ence and Engi neeri ng.

(1) WatersAComprehensiveTreatise; Franks, F., Ed.; Pl enum: New
York, 1972-1982; Vol s. 1-7.
(2) Sti l l i nger, F. H. Science1980, 209, 451-457.
(3) Water and Aqueous Solutions-Structure, Thermodynamics, and
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(12) I keda, S.; Takata, T.; Komoda, M.; Hara, M.; Kondo, J. N.; Domen,
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6851 Langmuir 2003, 19, 6851-6856
10.1021/l a034506h CCC: $25.00 2003 Ameri can Chemi cal Soci ety
Publ i shed on Web 07/18/2003
of i tem 2 above, usi ng pH and oxi dati on-reducti on
potenti al (ORP) measurements as our experi mental
probes.
Part 1 of thi s paper restri cts i tsel f tothe study of puri fi ed
(di sti l l ed and dei oni zed) water i n equi l i bri um wi th ai r,
wi thout added sal ts. Resul ts i ndi cate that both Hand H
i nfl uence the ki neti cs of equi l i brati on, that the needed
ti me scal e for such equi l i brati on i s l ong, and that enhanced
measurement preci si on i s needed. Part 2 descri bes
perturbi ng effects of some sol utes, ambi ent sti rri ng, and
l i ght. The tentati ve theoreti cal hypothesi s to account for
these envi ronmental magneti c effects i s that a di amag-
netophoresi s force i s operati ng i n the water sol uti on to
al ter the ki neti cs of the equi l i brati on process. Underscor-
i ng thi s concl usi on i s that, i n a zero H-fi el d envi ronment,
water proceeds toward equi l i bri um at an extremel y sl ow
rate and appears to get stuck for a l ong ti me i n a seri es
of i ntermedi ate metastabl e states.
Experimental Procedures
I n si mi l ar studi es, and i n chemi cal documents i n general , i t
i s often the ul ti mate equi l i bri um val ues or states that are
reported. Water encountered i n nature, however, i s rarel y at
chemi cal equi l i bri um, nor i s i t bei ng forced tostay at equi l i bri um.
Observati ons of the effects of el ectromagneti c or magneti c fi el ds
on water i n i ts progress toward equi l i bri um shoul d enhance our
pi cture of thei r i nteracti ons i n nature. Resul tant data may be
more di rectl y useful i n many fi el ds, such as engi neeri ng and
envi ronmental studi es. There i s a ri sk, natural l y, that some
uncontrol l ed factors may vary between sampl e and control
l ocati ons, causi ng a di fference i n thei r response. Mul ti pl e
measurements are necessary to average out such unwanted
effects.
I n thi s study, water was al l owed to move toward stabl e
equi l i bri um wi th ai r wi th mi ni mum i nterventi on, whi l e condi ti ons
other than magneti c exposure l evel s were kept as comparabl e as
possi bl e between sampl e and control . Ten or more measurements
were taken for each experi ment.
Sample Preparation. Di sti l l ed water and dei oni zed water
(ASTM type I water) were stored i n l oosel y l i dded l ab-grade
pol ypropyl ene jars for at l east 1 day before experi ments, for
equi l i brati on wi th ai r, unti l thei r pH reached the theoreti cal
val ue (about 5.7) for puri fi ed water saturated wi th CO2 at room
temperature and normal atmospheri c pressure. At thi s poi nt,
further pH change was sl ower than 0.005 pH uni ts per hour.
After thi s agi ng process, the same vol ume (250-300 mL)of water
was poured i nto each sampl e contai ner (l ab grade pol ypropyl ene
and acryl i c jars wi th screwed-on l i d). No sal ts were added to the
water sampl e pri or to the measurement. (Such puri fi ed water
cannot be consi dered tobe pure by todays standards, as i t contai ns
three oxygen i sotopes (oxygen-16, -17, and -18), several di ssol ved
gases, and orthoand para i somers of water i n an ortho/para rati o
that may vary from 10:1 to 3:1, dependi ng upon condi ti ons.)
Stirring.I n experi ments wi th sti rri ng, a sti rrer wi th a 55 cm
fi bergl ass shaft and a 3 cm nonmagneti c sti rri ng rod on the end
was used. When the sti rrer was turned on, the ac magneti c fl ux
at the l ocati on of the water sampl e changed by l ess than 0.2 mG.
Sothe effects of the ac fi el d generated by the sti rrers motor were
consi dered to be negl i gi bl e.
Temperature. The temperature dependence of gl ass pH
el ectrodes was corrected by the use of temperature compensati on
probes. The temperature of the water sampl e was al l owed to
shi ft natural l y wi th room temperature. The ai r temperature at
di fferent sampl e l ocati ons i n the l ab usual l y di ffered by <0.2 C.
The water temperature coul d fl uctuate up to 2 C duri ng the
fi rst few hours of the measurement. Beyond thi s i ni ti al peri od,
sl ow, di urnal change i n water temperature took pl ace, i denti cal
i n pattern and ampl i tude i n al l water sampl es.
Measurement Technique. Measurement of pH and ORP
was carri ed out wi th si x meters that had an i nput i mpedance of
>10
12
(Denver I nstruments pH, I SE conducti vi ty meter, model
225, and model 250 versi ons 1 and 2; Accumet model 150 ti trati on
control l er; Accumet AR50 dual channel pH/i on/conducti vi ty
meter, versi ons 1 and 2). Data val ues were sent from the meters
to a PC vi a RS-232. For pH, Ross combi nati on el ectrodes (Ori on
8102)and, for ORP, pl ati num el ectrodes (Ori on 96-78)were used.
Wi th careful groundi ng, al l measurements were conducted ei ther
i nsi de a Faraday cage i nsi de or a mu-metal cyl i nder. Background
noi se was (0.002 pH uni t for pH and (0.3 mV for ORP
measurement.
Calibration.The pH probes were cal i brated usi ng Ori on pure
water test ki t buffers, pH )4.10 and 6.98 (both (0.03 at 25 C),
for experi ments wi th l ow i oni c strength sol uti ons havi ng a
conducti vi ty of l ess than 100 S/cm. KCl sol uti on, suppl i ed wi th
the Ori on pure water test ki t toadjust the i oni cstrength of pure
water sampl es, was not added. For other sol uti ons, standard
buffers were used: Ori on pH ) 4.01, VWR pH ) 7.0, and VWR
pH )10.0 (al l (0.01 at 25 C). The cal i brati on sl ope wi ndow was
kept at 99.5-100.5%. The ORP probes were cal i brated rel ati ve
to each other. (Unti l recentl y, pH el ectrodes were notori ousl y
i naccurate i n sol uti ons of l ow i oni cstrength. Manufacturers today
have corrected thi s defi ci ency, and speci al el ectrodes are avai l abl e
for such sol uti ons.)
A bri ef descri pti on of the procedures devel oped toenhance the
measurement accuracy suffi ci ent for l ong-term pH and ORP
measurements i s gi ven i n the Supporti ng I nformati on secti on of
thi s arti cl e.
Results
1.Short/LongTime-ScaleBehavior.For twosampl es
of di sti l l ed water, A and B, Fi gure 1 i l l ustrates typi cal
short-ti me to l ong-ti me, respecti vel y, pH behavi or. As
di sti nct from background noi se, one typi cal l y notes two
types of fl uctuati ons for the fi rst few hours after the probes
have been i n pl ace: (i ) rapi d ( 1-3 s), smal l -ampl i tude
(0.01-0.03 pH uni ts or 1-3 mV for ORP) fl uctuati ons
that subsi de wi thi n a few mi nutes, and (i i ) sl ow ( 10-
30 mi n), l arge-ampl i tude (0.05-0.1 pH uni t or 60 mV
for ORP)fl uctuati ons that l ast for several hours. Readi ngs
duri ng the fi rst few mi nutes were occasi onal l y stabl e
wi thout fl uctuati ons of type i ; but type i i fl uctuati ons, of
l onger peri od, were al most al ways observed. The pH
readi ngs from two faul t-free probes i n di fferent sampl es
coul d have a l arge di fference at one moment and no
di fference 30 mi n l ater. ORP, on the other hand, tended
to fl uctuate more or l ess si mul taneousl y i n the same
di recti on for sampl es from a gi ven batch of di sti l l ed water.
A typi cal exampl e of thi s behavi or can be seen i n Fi gure
2. These sl ow/l arge-ampl i tude fl uctuati ons occurred i n-
dependentl y of temperature.
I t i s i mportant to note i n Fi gure l c the l ong-ti me l i near
pH sl ope regi me that devel oped for the two sampl es. I n
thi s exampl e, both sampl es were stored i n si mi l ar condi -
ti ons, and both devel oped nearl y the same sl ope and
i ntercept. Thi s l i near sl ope regi me, at l ong ti mes, i s very
characteri sti c for thi s type of water. A very si mi l ar type
of behavi or was observed wi th ORP measurements, that
i s, fl uctuati ons at short ti me and evol uti on to a constant
sl ope regi me after 5-10 h. For both pH and ORP, the
two parameters, sl ope and i ntercept, provi ded a val uabl e
tool for rel i abl y compari ng, at l ong ti me, smal l di fferences
between sampl es that were exposed to di fferent envi ron-
mental condi ti ons before the experi ment began. Rel i abi l i ty
of measurements l eadi ng to sl opes and i ntercepts was
regul arl y veri fi ed by shaki ng the sampl e to homogeni ze
i t, or by usi ng a second probe i n a di fferent regi on of the
same sampl e. Al so, el ectrode recal i brati on after the l ong-
ti me measurements showed that very l i ttl e absol ute
measurement error had occurred.
2.ZeroversusAmbient H-FieldExposure.For two
sampl es from the same batch of dei oni zed water, Fi gure
2 i l l ustrates the short-ti me and l ong-ti me behavi or as
i nfl uenced by ei ther an H ) 0 envi ronment (aged for 5
days i n a l ong mu-metal cyl i nder)or an ambi ent l aboratory
H-fi el d (aged for 5 days i n an el ectri cal l y grounded Faraday
6852 Langmuir, Vol. 19, No. 17, 2003 Yamashita et al.
cage), duri ng premeasurement storage. The ORP val ues
for these two sampl es di ffered by l ess than 2 mV at the
fourth mi nute, but thei r i ntercept di ffered by 40 mV i n
the l ong-term measurement. The fi tti ng equati ons i n
Fi gure 2b are for the ti me i nterval between the 25th and
37th hours. The chart reveal s that, after 40 h, these two
sampl es of water were sti l l a very l ong way from reachi ng
a possi bl e equi l i bri um condi ti on. From the sl ope val ues,
thi s mi ght requi re thousands of hours.
I n Fi gure 3, a pH compari son i s made for two sampl es
of dei oni zed water from the same batch, but measured i n
a Faraday cage wi th an ambi ent H-fi el d, versus twoother
sampl es from thi s same batch measured i n the mu-metal
cyl i nder. One notes that, al though the ambi ent fi el d
sampl es approach a common val ue after 14 h, the zero
fi el d sampl es do not. I n the zero H-fi el d case, the pH
appears to stay l ocked i n i ntermedi ate states for l ong
peri ods, wi thout change, before movi ng on toward some
i ndi vi dual end states for thi s 14 h ti me peri od.
3. Static Fluid/dc Magnetic Effect. To measure the
effects of a stati c magneti c fi el d on stati c water, pH was
measured for 20 h for sampl es of di sti l l ed water that were
si mul taneousl y exposed to a stati c magneti c fi el d. A bar
magnet of about 1000 G was attached to the bottom wal l
of one sampl e contai ner, as i n Fi gure 4. Water from the
same batch but wi thout a magnet served as a control , and
10 i ndi vi dual compari son tests were run. Separate ex-
peri ments were taken over a peri od of 2 months to
mi ni mi ze data bi as from varyi ng di sti l l ed water qual i ty
and other uncontrol l ed factors. Large vari ati on between
each run, as i ndi cated by the standard devi ati on, supports
thi s approach. Tabl e 1 l i sts the sl ope mean, medi an, and
range wi th standard devi ati on (STD). Al l the stati sti cs i n
thi s work were cal cul ated usi ng the students t-test for
2-tai l ed smal l sampl e anal ysi s unl ess otherwi se noted.
From these data i t seems cl ear that the presence of thi s
dc magnet caused the rate of pH change wi th ti me to
i ncrease. The acti on of thi s H-fi el d on pH evol uti on seemed
to end wi th the abrupt removal of the magnet.
4. MovingFluid/dc Magnet Effect. I n these experi -
ments pH was measured after the water was sti rred whi l e
bei ng exposed to a stati c magneti c fi el d for 3 mi n. The pH
was al so measured si mul taneousl y for a standi ng un-
sti rred water sampl e, to get a basel i ne, and for sti rred
water wi thout magneti c exposure, to see any change i n
pH caused by the sti rri ng al one. Separate measurements
were taken over a peri od of months.
The test water was sti rred for 3 mi n between two
permanent magnets (1000 G each) wi th opposi ng pol es.
Fi gure 5 i l l ustrates the dual dc magnet confi gurati on,
rel ati ve to the vessel of di sti l l ed water, as used for thi s
set of experi ments. Al umi num foi l was pl aced around the
sti rrer to mi ni mi ze contami nati on by dust. The control
(same water batch, but no magnets) was al so sti rred for
exactl y 3 mi n. The sampl es remai ned i n a Faraday cage
Figure1. (a) Typi cal pH measurement, fi rst 5 mi n. Apparent
stabi l i ty after 3 mi n of fl uctuati on. (Di sti l l ed water, 2 sampl es,
same batch and condi ti ons.) Meter: Denver 225 for Fi gures
1a-c. (b) Same pH measurement seri es as Fi gure 1a, fi rst 5 h.
Apparent stabi l i ty of Fi gure 1a actual l y was the start of sl ow,
l arge ampl i tude chaoti cfl uctuati ons. (c)Same pH measurement
seri es as Fi gures 1a and 1b, fi rst 2 days. Ordered l i near pattern,
and si mi l ari ty of sampl es, appear on thi s l ong-ti me scal e.
Figure 2. (a) ORP of water previ ousl y stored i n di fferent
condi ti ons, fi rst 4 mi n. Both readi ngs were stabl e and decep-
ti vel y si mi l ar i n short term. (Dei oni zed water stored 5 days i n
ambi ent fi el d and zero fi el d.) Meter: Denver 225 for Fi gures
2a and 2b. (b) ORP of water, same sampl es as Fi gure 2a, fi rst
40 h. Di fference between i ntercepts of l ong-ti me l i near trends
may refl ect di fferent sampl e storage condi ti ons.
pH and ORP Equilibration Rates of Water Langmuir, Vol. 19, No. 17, 2003 6853
duri ng sti rri ng. However, the l i d was taken off to l et the
l ong sti rri ng shaft through. Duri ng sti rri ng, the pH
el ectrodes were hung wi th just thei r ti ps i mmersed i n
water from the same batch i n another contai ner, toprevent
dryi ng. The magnets were l eft on the contai ner for a few
mi nutes after sti rri ng, duri ng whi ch pH measurement
began. Tabl e 2 provi des sl ope mean, medi an, and range
for these 10 compari sons. One can cl earl y see that, for pH
sl ope, (sti rri ng pl us magnets) > (sti rri ng al one) > (un-
sti rred, nomagnets). The mean pH sl ope, wi th thi s magnet
confi gurati on, was 1.6 ti mes l arger than that wi th
sti rri ng onl y.
Fi gure 6 i s provi ded to gi ve a more detai l ed pi cture of
one set of the raw pH data from whi ch Tabl e 2 was deri ved.
Sampl e A was sti rred wi th magnets present, whi l e sampl e
B was sti rred wi thout magnets. At about the 18 h poi nt,
both measurement probes were pl aced i n sampl e A, and
2 h l ater, both were pl aced i n sampl e B. Thi s tended to
confi rm the rel i abi l i ty of the probe measurements.
5. 60Hz EMFieldsversustheH ) 0Condition. I n
thi s set of experi ments, the pH was measured both duri ng
and after exposure to l ow i ntensi ty ac magneti c fi el ds
(hi gh fi el d (HF)wi th Bval ues of 40-120 mG, ambi ent
fi el d (AF) wi th B val ues of 3-9 mG, and zero fi el d
(ZF) wi th Bval ue of 0 mG). Two ac adapters, of the type
commonl y found i n resi dences and work pl aces, were used
as the 60 Hz source, wi th the fi el d i ntensi ty bei ng
measured by a tri axi al ac magneti c fl ux meter. I n these
experi ments, the sampl es were fi rst stored at thei r fi el d
exposure l ocati ons for 1-7 days, and then rel ocated to an
area where the magneti c fl ux was at ambi ent l evel (3-5
mG), for measurement.
For 12 sampl e pai rs of dei oni zed water from the same
batch, Tabl e 3 provi des ORP sl ope mean, medi an, and
range val ues for these 12 sampl e pai rs. One notes that,
on average, the ORP evol uti on rate for AF condi ti ons was
about twi ce that for ZF. Fi gure 7 provi des an exampl e
ti me course for ORPevol uti on i n these twofi el d categori es.
Note the very l ong metastabl e regi on (between hours 45
and 75) for the ZF case. I n the data on aqueous sol uti ons,
to be presented i n Part 2,
13
the HF case provi ded sti l l
hi gher sl opes than the AF case, for comparabl e evol uti on
ti mes, and appeared to asymptoti cal l y move toward zero
sl ope after about 5 days. The temperatures of the water
sampl es i n zero fi el d and ambi ent fi el d shi fted i n cl ose
paral l el , so the temperature shi ft was apparentl y not the
di rect cause of the di fferenti al behavi or of thei r ORP
val ues.
When these water sampl es were abruptl y sti rred i n the
ZF condi ti on compared to the AF condi ti on, there was
(13) Mendenhal l , W.; Beaver, R. J. I ntroduction to probability and
statistics, 8th ed.; PWS-Kent: Boston, 1991; Chapter 9, pp 322-391.
(14) Yamashi ta, M.; Duffi el d, C.; Ti l l er, W. A. DC magneti c fi el d and
el ectromagneti c fi el d effects on the pH and ORP equi l i brati on rates of
water; Part I I : Aqueous Sol uti ons. I n preparati on.
Table 1. pH Slope Variation with Static Magnetic Field
a
exposure condi ti on mean sl ope (pH/h) medi an sl ope (pH/h) sl ope range (pH/h)
wi th magnet 0.0063 (STD ) 0.002) 0.0057 0.002-0.0098
wi thout magnet 0.0048 (STD ) 0.003) 0.0047 0.000-0.0086
rati o 1.3 (STD ) 17) 1.2 0.68-55
a
p-val ue < 0.10. Ten sampl es of unsti rred di sti l l ed water for each exposure condi ti on.
Figure 3. (a) pH measured i n ambi ent magneti c fi el d. (Two
dei oni zed water sampl es measured i n Faraday cage.) Meter:
Denver 225. (b) pH measured i n zero magneti c fi el d. I n zero
fi el d, pH evol ved more sl owl y, and often stabi l i zed for an hour
or more at val ues where water di d not stabi l i ze i n the ambi ent
fi el d. (Two sampl es, same water batch as Fi gure 3a, measured
i n magneti cal l y shi el ded cyl i nder. Meter: AR 50. The four
measurements shown i n 3a and 3b were col l ected si mul ta-
neousl y.
Figure4. Water vessel and magnet pl acement for stati c-water/
dc-fi el d experi ments.
Figure 5. Water vessel and magnet pl acement for sti rred-
water/dc-fi el d experi ments. The l i d was removed, and the foi l
cover added duri ng sti rri ng wi th nonmagneti c sti rri ng bar.
6854 Langmuir, Vol. 19, No. 17, 2003 Yamashita et al.
general l y (i ) a l arger i mmedi ate change i n pH or ORP
l evel for the ZF compared to the AF, and (i i ) a sl ower
transi ti on back toa new, or the same, ti me-evol uti on curve
for the ZF compared tothe AF. Thi s behavi or can be readi l y
seen i n Fi gure 8. When one compared two sampl es from
the same batch i n the ZF envi ronment wi th sti rri ng, but
ei ther wi th or wi thout two dc magnets attached to the
vessel as i n Fi gure 5, a si gni fi cantl y l arger pH and ORP
sl ope al ways devel oped for the attached-magnets case.
Discussion
Several rather remarkabl e i nsi ghts concerni ng water
ari se from thi s fai rl y strai ghtforward and fai rl y l ow-tech
study. The fi rst i s that, even wi th hi ghl y puri fi ed water
(approxi matel y ASTM type I , here cal l ed dei oni zed water),
pH and ORPsl opes for sampl es from the same preparati on
batch can exhi bi t a wi de range of approxi matel y constant
sl opes at the 20 h moni tori ng poi nt i n the l ong-term
profi l e. Thi s may rel ate to H-bond structural di fferences,
Table 2. pH Slope Variation with Static Magnetic Field and Stirring
a
exposure condi ti on mean sl ope (pH/h) medi an sl ope (pH/h) sl ope range (pH/h)
sti rred wi th magnets 0.0075 (STD ) 0.003) 0.0081 0.0015-0.012
sti rred wi thout magnets 0.0065 (STD ) 0.003) 0.0064 0.0019-0.011
standi ng wi thout magnets 0.0037 (STD ) 0.0017) 0.0038 0.001-0.0065
a
Sl ope i s l arger wi th sti rri ng than wi thout (p-val ue < 0.025). The mean sl ope sti rred wi th magnet i s 1.64 ti mes l arger than that wi th
sti rri ng onl y ((0.94, p-val ue < 0.10). Di sti l l ed water; 10 sti rred sampl es i n each condi ti on.
Table 3. ORP Slope Is Greater for Ambient (AF) than Zero (ZF) Magnetic Field
a
exposure condi ti on mean sl ope (mV/h) medi an sl ope mV/h) sl ope range mV/h)
AF 0.16 (STD ) 0.07) 0.16 0.07-0.32
ZF 0.076 (STD ) 0.06) 0.049 0.011-0.17
rati o 3.75 (STD ) 2.70) 3.58 0.55-7.04
a
p-val ue < 0.005. Unsti rred dei oni zed water; 12 sampl es i n each condi ti on.
Figure6. pH of sti rred water, wi th and wi thout magnets. A
few mi nutes before t ) 0, sampl e A was sti rred between two
magnets and sampl e Bwas sti rred wi thout magnets. After l i near
trends devel oped, homogenei ty of water, and system rel i abi l i ty,
were demonstrated by swi tchi ng probes between sampl es.
(Di sti l l ed water.) Meter: Denver150.
Figure 7. Extremel y sl ow ORP equi l i brati on i n zero fi el d,
compared wi th ambi ent fi el d. I n zerofi el d, ORPoften stabi l i zed
at l evel s where i t woul d not, i f i n an ambi ent fi el d. (Dei oni zed
water, aged 4 days.) Meter:Denver250.
Figure8. (a)Larger pH change when sti rred i n zerofi el d than
i n ambi ent fi el d. (Dei oni zed water, stored 2 weeks under typi cal
condi ti ons before sti rri ng, and conti nued after.)Meter: Denver
250. (b)Large ORPchange when sti rred i n zerofi el d; nochange
i n ambi ent fi el d. (dei oni zed water.)Meter: Denver 150. (c)New
l evel of ORP, after sti rri ng i n zero fi el d, does not persi st i n thi s
exampl e. (dei oni zed water.) Meter: Denver250.
pH and ORP Equilibration Rates of Water Langmuir, Vol. 19, No. 17, 2003 6855
as di sti nct from chemi cal di fferences, between sampl es of
the same batch. Revi ewi ng the data shows the fol l owi ng
spreads of val ues: (1) The pH sl opes for the stati c water/
no dc magnet experi ment sampl es di ffered by a factor of
80. (2) The pH sl ope for the sti rred water/no dc magnet
sampl es di ffered by a factor of 10. (3)For the stati cwater/
wi th dc magnet case, the spread was a factor of 5. (4)For
the sti rred water/wi th dc magnet case, the spread was a
factor of 8. (5) For the ZF case, the spread was a factor
of 15.
The measurements i n Tabl es 1-3 were made wi th
di sti l l ed water and dei oni zed water, over a peri od of
months, duri ng whi ch the qual i ty of the water suppl y coul d
have vari ed. Even wi th the Mi l l i pore system, dependi ng
on the fi l ter condi ti on, there i s i nevi tabl e vari abi l i ty of
trace el ements over ti me.
The remarkabl e fact that pH and ORP measured i n ZF
appear to very sl owl y evol ve i n a seri es of qui te l ong-term
metastabl e states, i n both the upward and downward
di recti ons, poi nts tothe presence of appreci abl e acti vati on
barri ers for process ki neti cs that are somehow rel ated to
magneti c or EM fi el ds. Perhaps thi s ki nd of behavi or i s
rel ated to the morphol ogi cal nature of the waters hy-
drogen-bond structure. I f so, the degree of thi s structures
ri gi di ty versus mal l eabi l i ty may be i nti matel y i nvol ved
wi th a proton magneti c resonance-type phenomenon that
somehow enhances the fl exi bi l i ty and gl i ssi l e nature of
the H-bond network.
Long-ti me pH and ORP measurements appear to be
essenti al tocharacteri ze puri fi ed waters structural state,
as di sti nct from i ts chemi cal state. Of course, O
2
and CO
2
equi l i brati on of the sampl es wi th ambi ent ai r i s typi cal l y
a fai rl y sl ow process but can be speeded up consi derabl y
by sti rri ng. Thi s i s wel l understood. What i s not so wel l
understood i s the enhancement effect associ ated wi th the
presence of ei ther a dc magneti c fi el d or an ac EM fi el d.
Certai nl y, one expects di amagnetophoresi s-type forces
to be acti ng on the water sampl es vi a both dc magneti c
and ac EM fi el ds. I n addi ti on, for ac fi el ds, di el ectro-
phoresi s-type and magneti c resonance-type forces are
present. Al though such forces woul d enhance the effecti ve
di ffusi on coeffi ci ent for vari ous di pol ar moi eti es i n the
water, the unenhanced di ffusi on coeffi ci ents are suf-
fi ci entl y l arge (D 5 10
-6
cm
2
s
-1
) to al l ow di ffusi onal
mi xi ng over di stances of 0.1 cm i n 30 mi n. Thi s i s a
ti me much shorter than the phenomena we are deal i ng
wi th i n these experi ments, yet the ki neti c enhancement
effect i ncreases as the fi el d strength i ncreases. One must
al so consi der changes i n ortho/para water
15
rati o i n the
presence of magneti c fi el ds, as such changes are l i kel y to
i nfl uence both pH and ORP val ue.
More than hal f a century ago, i t was shown that the
conversi on rate between the ortho and para forms of
hydrogen i n a condensed phase was of second order.
16,17
Si l vera
18
i ndi cated that, for thi s to occur, si mul taneous
changes must happen i n (a)rotati onal angul ar momentum
by J ) 1 and (b) tri pl et and si ngl et nucl ear spi n states.
He al so poi nts to the observati on of O
2
i mpuri ti es i n H
2
as bei ng an extremel y effecti ve catal yst of the ortho/para
transi ti on to devel op a magneti c fi el d-screeni ng sphere of
para mol ecul es around each O
2
mol ecul e.
I l i sca and Pari s
19,20
have recentl y provi ded a new
el ectron-nucl eus resonant mechani sm to faci l i tate the
ortho/para conversi on process. However, at the H and
H val ues used i n thi s paper, these effects are expected to
be smal l and unl i kel y toexpl ai n the rather l arge pH effects
and ORP effect that we fi nd. On the other hand, i f we l ook
at Si l veras O
2
observati ons i n H
2
, i n di amagneti c water,
a si mi l ar thermodynami c dri vi ng force mi ght exi st to
generate H
+
i ons vi a the di ssoci ati on reacti on of H
2
O
whi ch, i n turn, screen the magneti c fi el d of the di ssol ved
O
2
speci es soas toul ti matel y i ncrease the O
2
and perhaps
al so the CO
2
reacti ons for water i n equi l i bri um wi th ai r
as H i ncreases.
Thi s bri ngs us tothe fi nal poi nt that common l aboratory
el ectri cal equi pment, i n regul ar use, provi des suffi ci entl y
strong fi el ds to sti mul ate thi s seemi ngl y anomal ous
behavi or of puri fi ed water. The i nfl uence of such devi ces,
used by the sci enti fi c communi ty i n thei r day-to-day
experi ments wi th aqueous sol uti ons and perhaps many
other fl ui ds, needs to be more careful l y studi ed and
understood.
Acknowledgment. Thi s work was parti al l y supported
by Di tron, LLC, and the Samuel i I nsti tute. The authors
wi sh tothank Professor Norm Sl eep and Dr. Wal ter Di bbl e,
Jr., for hel pful gui dance duri ng the course of thi s study,
Professor Ji m Lecki e for the use of hi s water puri fi cati on
system, and Gravi ty Probe B for the use of a magneti c
shi el d.
SupportingInformationAvailable: Bri ef descri pti on
of the procedures devel oped to enhance the measurement
accuracy suffi ci ent for l ong-term pH and ORP measurements.
Thi s materi al i s avai l abl e free of charge vi a the I nternet at
http://pubs.acs.org.
LA034506H
(15) Ti khonov, V. I .; Vol kov, A. A. Science2002, 296, 2363.
(16) Moti zuki , K.; Nagami ya, T. J . Phys. Soc. J pn. 1956, 11, 93-104.
(17) Peters, G.; Schramm, B. Ber. Bunsen-Ges. Phys. Chem. 1998,
102, 1857-1864.
(18) Si l vera, I . F. Rev. Mod. Phys. 1980, 52, 393-452.
(19) I l l i sca, E.; Pari s, S. Phys. Rev. Lett. 1999, 82, 1788-1791.
(20) Pari s, S.; I l l i sca, E. J . Phys. Chem. A 1999, 103, 4964-4968.
6856 Langmuir, Vol. 19, No. 17, 2003 Yamashita et al.